CN103570967A - Method for preparing regenerated cellulose spherical aerogel modified through carboxylation - Google Patents
Method for preparing regenerated cellulose spherical aerogel modified through carboxylation Download PDFInfo
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Abstract
The invention relates to a method for preparing regenerated cellulose spherical aerogel modified through carboxylation, which aims at the problem of poor adsorptive property of the cellulose aerogel prepared by the existing methods. The method comprises steps of firstly, mixing sodium hydroxide, urea and deionized water, then adding into a cellulose raw material, preparing a cellulose solution, adding the cellulose solution into a regeneration solution for solidifying, washing and obtaining spherical hydrogel; and secondly, dissolving TEMPO (tetramethyl-piperidin-1-oxyl) and sodium bromide into deionized water, adding the spherical hydrogel, then adding a sodium hypochlorite solution, regulating pH value of a system through a sodium hydroxide solution, steeping, exchanging the collected solid phase objects sequentially through absolute ethyl alcohol and a tertiary butanol solvent, then cooling, finally, freeze drying so as to finish preparing the cellulose spherical aerogel. The largest capacity of the obtained spherical aerogel in adsorbing metal ions Cu<2+> reaches 0.55m mol/g, and the adsorptive property is good.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose aerogels.
Background technology
Aerogel is that the liquid solvent in gelatinous material is replaced by air, and there is no significantly to change the porous material of himself network structure.In the thirties in 20th century, Kistler is synthetic SiO first
2aerogel, various aerogel materials are synthesized gradually subsequently, as aluminum oxide, rubber, derivatived cellulose etc.Aerogel has unique vesicular structure, as extremely-low density, high specific surface area, unique optics and acoustical behavior, low-k and extremely low thermal conductivity.And Mierocrystalline cellulose is that a kind of reserves are abundant, reproducible natural high moleculer eompound, it has good biocompatibility and structural stability.Therefore the aerogel material of preparing with Mierocrystalline cellulose is just rich in both common characteristics, increases that cellulose aerogels is functional just has very large feasibility and a practical significance by cellulose modified technology.But there is irreversible hydrogen bond association in existing cellulose aerogels cellulose molecular chain in drying process, cause the problems such as the large and network alligatoring in network space, meanwhile, Mierocrystalline cellulose self to the absorption property of metallic cation and cationic dyestuff a little less than.
Summary of the invention
The object of the invention is the weak problem of cellulose aerogels absorption property obtaining in order to solve existing preparation method, and the preparation method of the spherical aerogel of a kind of carboxylated modification regeneration Mierocrystalline cellulose is provided.
The preparation method of the spherical aerogel of the carboxylated modification regeneration Mierocrystalline cellulose of the present invention follows these steps to realize:
One, be in mass ratio (6～7): (10～12): (70～81) mix sodium hydroxide, urea and deionized water, at the temperature of-15～-12 ℃, add cellulosic material, stirring and dissolving is removed insoluble throw out by centrifugal treating and is obtained cellulose solution, then cellulose solution is dropwise joined in regeneration soln with dropper, solidify 5～15min in regeneration soln after, collect spherical hydrogel, spherical hydrogel is dipped in deionized water with after deionized water wash 3～5 times, obtains regenerated cellulose spherical hydrogel standby;
Two, by 1～1.5mg TEMPO(2, 2, 6, 6-tetramethyl piperidine-1-oxygen base) and 10～15mg Sodium Bromide dissolve in 30～50mL deionized water, the regenerated cellulose spherical hydrogel that adds 10～20g step 1 to obtain, and then to add 3～4mL massfraction be 11% chlorine bleach liquor, by 0.5mol/L sodium hydroxide solution regulation system pH to 9～12, after soaking 6～24h, collect solid formation, solid formation joins and in dehydrated alcohol, soaks 3～4h, by dehydrated alcohol and t-butanol solvent, exchange 3～5 times successively again, solid phase gel after exchange obtains freezing gel after freezing 22～26h at-20～-15 ℃, lyophilize 22～26h under the condition that finally freezing gel to be placed in to condenser temperature and to be-56～-50 ℃ and vacuum tightness be 300Pa, obtain the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose,
Regeneration soln described in its step 1 is (2～3) by volume ratio: (2～3): the ethyl acetate of (0.5～1), trichloromethane and acetic acid form.
The method that the present invention prepares the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose is to utilize TEMPO oxide treatment to increase the perviousness on the spherical aerogel of regenerated cellulose surface, and the gathering of having avoided internal network to produce because of dry and hydrogen bond association, the introducing of carboxyl simultaneously makes the spherical aerogel of regenerated cellulose improve to the absorption property of cationic dyestuff and part metals ion, the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose making is 1.24mmol/g to the maximal absorptive capacity of auramine O, to metal ion Cu
2+maximal absorptive capacity be 0.55mmol/g.The present invention is mainly used in absorption and catalytic field.
Accompanying drawing explanation
The outside drawing with reference to sample SRCA-0 hydrogel that Fig. 1 is prepared for comparative example;
Fig. 2 obtains the outside drawing of hydrogel after step 2 immersion 6h in embodiment mono-;
Fig. 3 obtains the outside drawing of hydrogel after step 2 immersion 12h in embodiment bis-;
Fig. 4 obtains the outside drawing of hydrogel after step 2 immersion 24h in embodiment tri-;
The surface tissue figure with reference to sample SRCA-0 aerogel that Fig. 5 is prepared for comparative example;
Fig. 6 is the surface tissue figure of the modified sample SRCA-1 aerogel of embodiment mono-preparation;
Fig. 7 is the surface tissue figure of the modified sample SRCA-2 aerogel of embodiment bis-preparations;
Fig. 8 is the surface tissue figure of the modified sample SRCA-3 aerogel of embodiment tri-preparations;
The cut-away view with reference to sample SRCA-0 aerogel that Fig. 9 is prepared for comparative example;
Figure 10 is the cut-away view of the modified sample SRCA-1 aerogel of embodiment mono-preparation;
Figure 11 is the cut-away view of the modified sample SRCA-2 aerogel of embodiment bis-preparations;
Figure 12 is the cut-away view of the modified sample SRCA-3 aerogel of embodiment tri-preparations;
Figure 13 is the Fourier transform infrared spectrogram of four kinds of sample gas gels of comparative example, embodiment mono-, embodiment bis-, embodiment tri-preparations, wherein 1-with reference to sample SRCA-0 aerogel, 2-modified sample SRCA-1 aerogel, 3-modified sample SRCA-2 aerogel, 4-modified sample SRCA-3 aerogel;
Figure 14 is the absorption histogram of four kinds of sample gas gels of comparative example, embodiment mono-, embodiment bis-, embodiment tri-preparations;
Figure 15 is the adsorptive capacity histogram to metal ion with reference to sample SRCA-0 aerogel and modified sample SRCA-2 aerogel, 1-with reference to sample SRCA-0 aerogel, 2-modified sample SRCA-2 aerogel.
Embodiment
Embodiment one: the preparation method of the spherical aerogel of the carboxylated modification regeneration Mierocrystalline cellulose of present embodiment follows these steps to implement:
One, be in mass ratio (6～7): (10～12): (70～81) mix sodium hydroxide, urea and deionized water, at the temperature of-15～-12 ℃, add cellulosic material, stirring and dissolving is removed insoluble throw out by centrifugal treating and is obtained cellulose solution, then cellulose solution is dropwise joined in regeneration soln with dropper, solidify 5～15min in regeneration soln after, collect spherical hydrogel, spherical hydrogel is dipped in deionized water with after deionized water wash 3～5 times, obtains regenerated cellulose spherical hydrogel standby;
Two, by 1～1.5mg TEMPO(2, 2, 6, 6-tetramethyl piperidine-1-oxygen base) and 10～15mg Sodium Bromide dissolve in 30～50mL deionized water, the regenerated cellulose spherical hydrogel that adds 10～20g step 1 to obtain, and then to add 3～4mL massfraction be 11% chlorine bleach liquor, by 0.5mol/L sodium hydroxide solution regulation system pH to 9～12, after soaking 6～24h, collect solid formation, solid formation joins and in dehydrated alcohol, soaks 3～4h, by dehydrated alcohol and t-butanol solvent, exchange 3～5 times successively again, solid phase gel after exchange obtains freezing gel after freezing 22～26h at-20～-15 ℃, lyophilize 22～26h under the condition that finally freezing gel to be placed in to condenser temperature and to be-56～-50 ℃ and vacuum tightness be 300Pa, obtain the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose,
Regeneration soln described in its step 1 is (2～3) by volume ratio: (2～3): the ethyl acetate of (0.5～1), trichloromethane and acetic acid form.
The preparation of present embodiment step 1 regenerated cellulose spherical hydrogel adopts anti-liquid phase sessile drop method to be prepared.The immersion process that step 2 is carried out after by 0.5mol/L sodium hydroxide solution regulation system pH value is the oxide treatment of at room temperature carrying out.
Preparation method described in present embodiment adopts 2,2,6,6-tetramethyl piperidine-1-oxygen base (TEMPO) to carry out carboxylated modification to cellulose aquagel, and preparation technology is simple, easy to operate, has improved the performance of cellulose aerogels absorption.
Embodiment two: what present embodiment was different from embodiment one is that step 1 is sodium hydroxide, urea and deionized water to be mixed in 7: 12: 81 in mass ratio.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is that cellulosic material described in step 1 is bamboo fibers, and the Mierocrystalline cellulose quality mark of bamboo fibers is 98%.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that stirring in the stirring and dissolving described in step 1 is that rotating speed with 500r/min carries out magnetic agitation.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that step 2 is passed through 0.5mol/L sodium hydroxide solution regulation system pH to 10.5, collects solid formation after immersion 12h.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that step 2 exchanges 3～5 times by dehydrated alcohol and t-butanol solvent more successively, each is 10～13h in the swap time of anhydrous ethanol solvent, and be 10～13h each swap time in t-butanol solvent.Other step and parameter are identical with one of embodiment one to five.
Comparative example: the present embodiment follows these steps to implement with reference to the preparation method of sample SRCA-0:
7g sodium hydroxide, 12g urea and 81g deionized water are mixed, at the temperature of-12 ℃, add 2g natural bamboo fibres, with the dissolving of 500r/min rotating speed magnetic agitation, by centrifugal treating, remove insoluble throw out and obtain cellulose solution, then cellulose solution is dropwise joined in regeneration soln with dropper, solidify 5min in regeneration soln after, collect spherical hydrogel, spherical hydrogel is dipped in deionized water with after deionized water wash 3 times, obtains the hydrogel with reference to sample SRCA-0; Then by dehydrated alcohol and t-butanol solvent, exchange 3 times successively, solid phase gel after exchange obtains freezing gel at-20 ℃ after freezing 24h, finally freezing gel is placed in to condenser temperature for lyophilize 24h under-54 ℃ and the vacuum tightness condition that is 300Pa, obtains the aerogel with reference to sample SRCA-0.
Wherein said regeneration soln is comprised of the acetic acid of the ethyl acetate of 150mL, the trichloromethane of 150mL and 10mL.
As shown in Figure 1, with reference to sample SRCA-0 aerogel surface tissue figure as shown in Figure 5, aerogel cut-away view as shown in Figure 9 for the outside drawing with reference to sample SRCA-0 hydrogel that the present embodiment obtains.
Embodiment mono-: the preparation method of the present embodiment modified sample SRCA-1 aerogel follows these steps to implement:
One, 7g sodium hydroxide, 12g urea and 81g deionized water are mixed, at the temperature of-12 ℃, add 2g natural bamboo fibres, with the dissolving of 500r/min rotating speed magnetic agitation, by centrifugal treating, remove insoluble throw out and obtain cellulose solution, then cellulose solution is dropwise joined in regeneration soln with dropper, solidify 5min in regeneration soln after, collect spherical hydrogel, spherical hydrogel is dipped in deionized water with after deionized water wash 3 times, obtains regenerated cellulose spherical hydrogel standby;
Two, by 1.25mg TEMPO(2, 2, 6, 6-tetramethyl piperidine-1-oxygen base) and 12.5mg Sodium Bromide dissolve in 37.5mL deionized water, the regenerated cellulose spherical hydrogel that adds 20g step 1 to obtain, and then to add 3.5mL massfraction be 11% chlorine bleach liquor, by 0.5mol/L sodium hydroxide solution regulation system pH to 10.5, after soaking 6h, collect solid formation, solid formation joins and in dehydrated alcohol, soaks 3h, by dehydrated alcohol and t-butanol solvent, exchange 3 times successively again, solid phase gel after exchange obtains freezing gel at-20 ℃ after freezing 24h, finally freezing gel is placed in to condenser temperature for lyophilize 24h under-54 ℃ and the vacuum tightness condition that is 300Pa, obtain modified sample SRCA-1 aerogel,
Wherein the regeneration soln described in step 1 is comprised of the acetic acid of the ethyl acetate of 150mL, the trichloromethane of 150mL and 10mL.
After the present embodiment step 2 immersion 6h, obtain the outside drawing of hydrogel as shown in Figure 2.As shown in Figure 6, aerogel cut-away view as shown in figure 10 for the surface tissue figure of modified sample SRCA-1 aerogel.
Embodiment bis-: what the preparation method of the present embodiment modified sample SRCA-2 aerogel was different from embodiment mono-is that step 2 is passed through 0.5mol/L sodium hydroxide solution regulation system pH to 10.5, collect solid formation after soaking 12h.Other step and parameter are identical with embodiment mono-.
After the present embodiment immersion 12h, obtain the outside drawing of hydrogel as shown in Figure 3.The modified sample SRCA-2 that modification time is controlled at 12h as we know from the figure can guarantee the stability of regenerated cellulose spherical hydrogel structure and higher carboxyl-content.As shown in Figure 7, aerogel cut-away view as shown in figure 11 for the surface tissue figure of modified sample SRCA-2 aerogel.
Embodiment tri-: what the preparation method of the present embodiment modified sample SRCA-3 aerogel was different from embodiment mono-is that step 2 is passed through 0.5mol/L sodium hydroxide solution regulation system pH to 10.5, collect solid formation after soaking 24h.Other step and parameter are identical with embodiment mono-.
After the present embodiment immersion 24h, obtain the outside drawing of hydrogel as shown in Figure 4.The surface tissue figure of modified sample SRCA-3 aerogel as shown in Figure 8, aerogel cut-away view as shown in figure 12, by the known surface tissue of this figure, along with increasing surface void, increases oxidization time, the network structure of the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose, has greatly improved to its surperficial permeability.
The Fourier transform infrared spectrogram of four kinds of sample gas gels of comparative example, embodiment mono-～embodiment tri-preparations as shown in figure 13, by the known modified sample of this figure than unmodified with reference to sample at 3380cm
-1place-OH stretching vibration absorption peak weakens; At 1737cm
-1there is the stretching vibration absorption peak of C=O in place's modified sample, and along with the increase peak intensity of modification time increases.The hydroxyl of these change list light fibers element molecules C6 is converted into carboxyl by the selective catalytic oxidation of TEMPO, and along with the increase carboxyl-content of modification time also increases gradually, further proved that TEMPO catalyzed oxidation plays carboxylated modifying function to the spherical aerogel of regenerated cellulose.
Four kinds of sample gas gels of comparative example, embodiment mono-～embodiment tri-preparations to the absorption histogram of auramine O as shown in figure 14, by the spherical aerogel of the carboxylated modification regeneration Mierocrystalline cellulose of the known increase along with the carboxylated degree in surface of this figure, show stronger adsorptive power, the color that is adsorbed solution shoals gradually.The unmodified adsorptive capacity with reference to sample SRCA-0 aerogel is 0.13mmol/g, and the adsorptive capacity of the sample SRCA-3 aerogel of process 24h modification is 1.24mmol/g.
With reference to sample SRCA-0 aerogel and modified sample SRCA-2 aerogel, the histogram of the adsorptive capacity of metal ion is shown in shown in 15, the sample SRCA-2 aerogel by the known modification 12h of this figure is to metal ion Cu
2+, Ni
2+, Pb
2+, Cd
2+and Zn
2+maximal absorptive capacity be respectively 0.55mmol/g, 0.41mmol/g, 0.43mmol/g, 0.45mmol/g and 0.33mmol/g.
Claims (6)
1. a preparation method for the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose, is characterized in that the preparation method of the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose follows these steps to realize:
One, be in mass ratio (6～7): (10～12): (70～81) mix sodium hydroxide, urea and deionized water, at the temperature of-15～-12 ℃, add cellulosic material, stirring and dissolving is removed insoluble throw out by centrifugal treating and is obtained cellulose solution, then cellulose solution is dropwise joined in regeneration soln with dropper, solidify 5～15min in regeneration soln after, collect spherical hydrogel, spherical hydrogel is dipped in deionized water with after deionized water wash 3～5 times, obtains regenerated cellulose spherical hydrogel standby;
Two, 1～1.5mg TEMPO and 10～15mg Sodium Bromide are dissolved in 30～50mL deionized water, the regenerated cellulose spherical hydrogel that adds 10～20g step 1 to obtain, and then to add 3～4mL massfraction be 11% chlorine bleach liquor, by 0.5mol/L sodium hydroxide solution regulation system pH to 9～12, after soaking 6～24h, collect solid formation, solid formation joins and in dehydrated alcohol, soaks 3～4h, by dehydrated alcohol and t-butanol solvent, exchange 3～5 times successively again, solid phase gel after exchange obtains freezing gel after freezing 22～26h at-20～-15 ℃, lyophilize 22～26h under the condition that finally freezing gel to be placed in to condenser temperature and to be-56～-50 ℃ and vacuum tightness be 300Pa, obtain the spherical aerogel of carboxylated modification regeneration Mierocrystalline cellulose,
Regeneration soln described in its step 1 is (2～3) by volume ratio: (2～3): the ethyl acetate of (0.5～1), trichloromethane and acetic acid form.
2. the preparation method of the spherical aerogel of a kind of carboxylated modification regeneration Mierocrystalline cellulose according to claim 1, is characterized in that step 1 is sodium hydroxide, urea and deionized water to be mixed in 7: 12: 81 in mass ratio.
3. the preparation method of the spherical aerogel of a kind of carboxylated modification regeneration Mierocrystalline cellulose according to claim 1, is characterized in that the cellulosic material described in step 1 is bamboo fibers, and the Mierocrystalline cellulose quality mark of bamboo fibers is 98%.
4. the preparation method of the spherical aerogel of a kind of carboxylated modification regeneration Mierocrystalline cellulose according to claim 1, is characterized in that stirring in the stirring and dissolving described in step 1 is that rotating speed with 500r/min carries out magnetic agitation.
5. the preparation method of the spherical aerogel of a kind of carboxylated modification regeneration Mierocrystalline cellulose according to claim 1, is characterized in that step 2 passes through 0.5mol/L sodium hydroxide solution regulation system pH to 10.5, collects solid formation after soaking 12h.
6. the preparation method of the spherical aerogel of a kind of carboxylated modification regeneration Mierocrystalline cellulose according to claim 1, it is characterized in that step 2 exchanges 3～5 times by dehydrated alcohol and t-butanol solvent more successively, each is 10～13h in the swap time of anhydrous ethanol solvent, and be 10～13h each swap time in t-butanol solvent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104387617A (en) * | 2014-10-30 | 2015-03-04 | 昆明理工大学 | Preparation method of corn stalk modified cellulose gel |
| CN104761749A (en) * | 2015-04-03 | 2015-07-08 | 四川大学 | Cellulose nanofiber hyperbranched modification method |
| CN106040184A (en) * | 2016-06-01 | 2016-10-26 | 齐鲁工业大学 | Preparation method of modified porous magnetic cellulose balls for adsorbing Cu<2+> |
| CN106589444A (en) * | 2016-12-23 | 2017-04-26 | 福州大学 | Method for preparing magnetic cellulose aerogel by utilizing waste paper |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285838A (en) * | 2013-07-02 | 2013-09-11 | 景德镇陶瓷学院 | Preparation method of functional magnetic absorbent used for treating industrial wastewater |
| CN103319746A (en) * | 2013-07-12 | 2013-09-25 | 东北林业大学 | Preparation method for spherical cellulose aerogel |
-
2013
- 2013-10-17 CN CN201310487510.1A patent/CN103570967A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285838A (en) * | 2013-07-02 | 2013-09-11 | 景德镇陶瓷学院 | Preparation method of functional magnetic absorbent used for treating industrial wastewater |
| CN103319746A (en) * | 2013-07-12 | 2013-09-25 | 东北林业大学 | Preparation method for spherical cellulose aerogel |
Non-Patent Citations (1)
| Title |
|---|
| NORIYUKI ISOBE ET AL.: "TEMPO-oxidized cellulose hydrogel as a high-capacity and reusable heavy metal ion adsorbent", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 26, 20 May 2013 (2013-05-20), pages 195 - 201 * |
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Application publication date: 20140212 |