CN109364889B - Preparation method and application of temperature-sensitive hydrogel - Google Patents
Preparation method and application of temperature-sensitive hydrogel Download PDFInfo
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- CN109364889B CN109364889B CN201811214515.6A CN201811214515A CN109364889B CN 109364889 B CN109364889 B CN 109364889B CN 201811214515 A CN201811214515 A CN 201811214515A CN 109364889 B CN109364889 B CN 109364889B
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- 238000001179 sorption measurement Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 15
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- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
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Abstract
The invention discloses a preparation method of temperature-sensitive hydrogel, which comprises the following steps: preparing cellulose acetate nanofibers; deacetylating the cellulose acetate nano-fibers by using alkali liquor to obtain cellulose nano-fibers; preparing cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel by using the cellulose nanofiber; grafting the cellulose nano-fiber with poly (N-isopropyl acryloyl)Soaking amine-co-maleic anhydride) hydrogel in a mixed solution of ferrous chloride and ferric chloride, adding ammonia water for reaction to obtain cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride)/Fe3O4The magnetic nanofiber composite hydrogel is the temperature-sensitive hydrogel. Compared with the prior art, the invention has the following beneficial effects: the invention prepares the cellulose nano-fiber by the thermally induced phase separation method, has simple process and high yield, and is very suitable for industrialized production.
Description
Technical Field
The invention relates to a preparation method of temperature-sensitive hydrogel, belonging to the technical field of porous adsorption materials.
Background
Heavy metal means a density of greater than 4.5m2The metal element per gram, such as Cu, Ag, Cr, Pb, etc. Heavy metal ions are discharged into water mainly through chemical production, chemical fertilizers and pesticides, domestic wastewater, mine exploitation and the like, and when the concentration of the heavy metal ions in the water exceeds the self-purification capacity of the water body, the heavy metal pollution of the water body is caused. With the rapid development of industry and agriculture, a large amount of heavy metal wastewater is discharged, and heavy metal pollution becomes one of the biggest hazards of environmental pollution. Heavy metals are not easily degraded under natural conditions, and are enriched in human bodies through food chains, so that the domestic heavy metal water pollution events are frequent in the last decade, and the problem of heavy metal pollution is not easy to solve. At present, the pollution to heavy metals is mainly carried out by chemical methods, such as a chemical precipitation method and an oxidation-reduction method; biological methods such as phytoremediation, biosorption and bioflocculation; physical methods such as separation, ion exchange and adsorption. The adsorption method has the advantages of rich source of adsorbent, low cost, large adsorption capacity, high treatment efficiency, and simple processEasy operation, no secondary pollution and the like, and is widely applied to the treatment of heavy metal ion wastewater. Conventional adsorbents have some deficiencies in selectivity and recycling. The currently studied adsorbents try to combine a plurality of adsorption materials by a physical doping or chemical connection method, and utilize the structural advantages of each material to prepare the adsorption material with high adsorption capacity, strong adaptability and convenient recycling.
The hydrogel is a solid material formed by mutually intertwining hydrophilic polymers through physical or chemical crosslinking to form a three-dimensional network structure, and water is used as a dispersion medium to fill the pores of the whole network structure. The hydrogel has unique advantages in the aspect of removing heavy metals as a high polymer material with a three-dimensional network structure. The intelligent hydrogel has responsiveness to external stimuli (such as temperature, pH, ionic strength, electric field strength and the like), so that the adsorption process of the hydrogel on heavy metal ions can be regulated and controlled by changing the external environment by using the intelligent hydrogel as an adsorbent, or the heavy metal ions are identified according to the special responsiveness of the hydrogel.
The natural polymer hydrogel has rich sources, low price and good biocompatibility, is widely applied to hydrogel preparation, but has poor stability, so the actual requirements of the hydrogel are often improved by blending or graft copolymerization of natural polymers and synthetic polymers and the like. However, most natural polymers are in a powder, block or film structure, and have low porosity and small specific surface area, and after grafting modification, the problems of low porosity, small specific surface area and the like still exist, so that the adsorption capacity of the natural polymers on heavy metal ions is low. How to improve the adsorption capacity of heavy metal ions becomes a key problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method and application of temperature-sensitive hydrogel. The invention is realized by the following technical scheme:
a preparation method of temperature-sensitive hydrogel comprises the following steps:
preparing cellulose acetate nanofibers;
deacetylating the cellulose acetate nano-fibers by using alkali liquor to obtain cellulose nano-fibers;
preparing cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel by using the cellulose nanofiber;
grafting the cellulose nanofibers with poly (N)-Isopropyl acrylamide-co-maleic anhydride) hydrogel is soaked in a mixed solution of ferrous chloride and ferric chloride, ammonia water is added for reaction, and cellulose nanofiber grafted poly (N-isopropyl acrylamide-co-maleic anhydride)/Fe is obtained3O4The magnetic nanofiber composite hydrogel is the temperature-sensitive hydrogel.
Preferably, the preparation method of the cellulose acetate nanofiber comprises the following steps:
dissolving cellulose acetate in a mixed solvent of tetrahydrofuran and N, N '-dimethylformamide to obtain a quenching liquid, quenching the quenching liquid at the temperature of-30 to-15 ℃, washing with distilled water to remove the tetrahydrofuran and the N, N' -dimethylformamide, and freeze-drying to obtain the cellulose acetate nanofiber.
Preferably, in the quenching liquid, the weight parts of the cellulose acetate, the tetrahydrofuran and the N, N' -dimethylformamide are 0.2-0.5 part, 1-3 parts and 5-10 parts respectively.
As a preferable scheme, the alkali liquor is an ethanol solution of NaOH, wherein the concentration of the NaOH is 0.1-0.2 mol/L.
Preferably, the preparation method of the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel comprises the following steps:
dissolving N-isopropyl acrylamide, maleic anhydride and N, N' -methylene bisacrylamide in a nitric acid solution to obtain a reaction solution A;
dissolving ammonium ceric nitrate in a nitric acid solution, and adding vinyl modified silicon dioxide and the cellulose nanofiber to obtain a reaction solution B;
dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at 30-60 ℃, sequentially washing with distilled water, performing Soxhlet extraction with acetone, and performing suction filtration to obtain the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel.
Preferably, in the reaction solution a: the weight parts of N-isopropyl acrylamide, maleic anhydride and N, N' -methylene bisacrylamide are respectively 5-10 parts, 2-3 parts and 0.05-0.1 part; in the reaction solution B: the weight parts of the ammonium ceric nitrate, the cellulose nano-fiber and the vinyl modified silicon dioxide are respectively 1-3 parts, 2-6 parts and 0.2-0.5 part.
Preferably, the preparation method of the vinyl modified silica comprises the following steps: reacting the vinyltriethoxysilane with silicon dioxide to obtain the vinyl modified silicon dioxide.
Preferably, in the mixed solution of the ferrous chloride and the ferric chloride, the molar ratio of the ferrous chloride to the ferric chloride is 1: 2; the concentration of the ammonia water is 1 mol/L.
An application of the temperature-sensitive hydrogel obtained by the preparation method in heavy metal ion adsorption.
Preferably, the heavy metal ions are copper ions.
The mechanism of the invention is as follows:
cellulose nanofibers were prepared by a thermally induced phase separation method. N-isopropylacrylamide and maleic anhydride were copolymerized onto the cellulose chain by free-radical initiated polymerization. And finally, compounding magnetic ferroferric oxide onto the hydrogel by a coprecipitation method.
The amino on the N-isopropyl acrylamide and the carboxyl generated after the hydrolysis of the maleic anhydride are utilized to perform the adsorption effect on the coordination chelation of the copper ions. The high porosity and large specific surface area of the cellulose nano-fiber are utilized to improve the adsorption capacity of the cellulose nano-fiber. Using Fe on hydrogel3O4The magnetic property of the hydrogel is beneficial to recycling after the hydrogel is adsorbed. The vinyl modified silica is added to improve the porosity of the hydrogel and the swelling rate and adsorption capacity of the hydrogel.
Compared with the prior art, the invention has the following beneficial effects:
1. n-isopropyl acrylamide and maleic anhydride are grafted to the cellulose nanofiber with biocompatibility, so that the volume size of the hydrogel is reduced, the specific surface area and the porosity are increased, the swelling rate is greatly improved, and the adsorption capacity of copper ions is improved;
2. the addition of the vinyl modified silicon dioxide forms a discontinuous network pore structure, so that the porosity is improved, the swelling rate is improved, and the adsorption capacity is improved;
3. the cellulose nano-fiber is prepared by the thermally induced phase separation method, the process is simple, the yield is high, and the method is very suitable for industrial production.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 cellulose nanofiber graft poly (N-isopropylacrylamide-co-maleic anhydride)/Fe prepared in example 1 of the present invention3O4Scanning electron microscope images of the magnetic composite hydrogel;
FIG. 2 cellulose nanofiber graft poly (N-isopropylacrylamide-co-maleic anhydride)/Fe prepared in example 1 of the present invention3O4The relationship between the temperature and the swelling ratio of the magnetic composite hydrogel;
FIG. 3 cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride)/Fe prepared in example 1 of the present invention3O4Adsorption kinetics curve of magnetic composite hydrogel.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
1) Preparation of cellulose nanofibers
1g of tetrahydrofuran and 10g N, N' -dimethylformamide were added to a serum bottle, and then 0.3g of cellulose acetate was added and dissolved with stirring to form a clear and transparent solution. The solution was poured into a petri dish and frozen in a freezer at-20 ℃ for 3 h. After the reaction is finished, the mixture is taken out and put into an ice-water mixture, and distilled water is replaced every 6 hours for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.1mol/L NaOH/ethanol solution for 24h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) And (3) preparing the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel.
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
Dissolving 0.6g N-isopropyl acrylamide, 0.2g maleic anhydride and 0.008g N, N' -methylene bisacrylamide in 15mL of 1mol/L nitric acid solution to obtain reaction liquid A; dissolving 0.1g of ammonium ceric nitrate in 15mL of 1mol/L nitric acid solution, and adding 0.2g of cellulose nanofiber and 0.03g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at the temperature of 50 ℃ for 4 hours, washing with distilled water, performing Soxhlet extraction with acetone, and performing suction filtration to obtain the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel, which is abbreviated as Cell-g-P (NIPAm-co-MA) nanofiber hydrogel.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4And (3) preparing the magnetic nanofiber composite hydrogel.
0.3g of Cell-g-P (NIPAm-co-MA) hydrogel is soaked in 100mL of ferrous chloride (0.0852g) and ferric chloride (0.2316g) solution, 10mL of 1mol/L ammonia water is added, and reaction is carried out for 9h to obtain Cell-g-P (NIPAm-co-MA)/Fe3O4The magnetic nanofiber composite hydrogel is temperature-sensitive hydrogel for copper ion adsorption.
Cell-g-P(NIPAm-co-MA)/Fe3O4The scanning electron microscope image of the magnetic nanofiber composite hydrogel is shown in FIG. 1, the hydrogel is in a porous fibrous structure, the fiber diameter is 178 +/-100 nm, and the porosity and the specific surface area of the hydrogel are 93.8% and 24.4m respectively2(ii) a magnetization of 0.022 emu/g. FIG. 2 shows Cell-g-P (NIPAm-co-MA)/Fe3O4Swelling ratio of magnetic nanofiber composite hydrogel changing with temperature curve of Cell-g-P (NIPAm-co-MA)/Fe3O4The magnetic nanofiber composite hydrogel begins to rapidly lose water at 28 ℃, reaches equilibrium at about 40 ℃, and has good temperature sensitivity near 36.2 ℃.
50mL of Cu with a concentration of 500mg/L2+The solution was added to an erlenmeyer flask and the pH adjusted to 7.0 with NaOH or HCl. Adding 10mg hydrogel into the above solution, shaking in constant temperature water bath at 25 deg.C for 10, 20, 50, 100, 200, 300, 400, 500, 800, 1200 and 1500min, and filtering supernatant. Measuring Cu in solution by atomic absorption spectrometer2+Concentration, calculating Cu in the adsorbed solution2+The concentration, adsorption curve is shown in FIG. 3. Within 0-300min, the adsorption quantity increases rapidly along with the adsorption time, the adsorption quantity gradually slows down in 300-500min, the adsorption balance is reached after 500min, and the fiber hydrogel can adsorb Cu2+The saturated adsorption amount of (A) was 390.2 mg/g.
Example 2
1) Preparation of cellulose nanofibers
2g tetrahydrofuran and 8g N, N' -dimethylformamide were added to a serum bottle, and then 0.2g cellulose acetate was added and dissolved with stirring to form a clear and transparent solution. The solution was poured into a petri dish and chilled in a refrigerator at-25 ℃ for 2.5 h. After the reaction is finished, the mixture is taken out and put into an ice-water mixture, and distilled water is replaced every 6 hours for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.15mol/L NaOH/ethanol solution for 24h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) And (3) preparing the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel.
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
Dissolving 0.4g N-isopropyl acrylamide, 0.28g maleic anhydride and 0.01g N, N' -methylene bisacrylamide in 15mL of 1mol/L nitric acid solution to obtain reaction liquid A; dissolving 0.3g of ammonium ceric nitrate in 15mL of 1mol/L nitric acid solution, and adding 0.3g of cellulose nanofiber and 0.04g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting for 3 hours at the reaction temperature of 45 ℃, washing with distilled water, performing Soxhlet extraction with acetone, and performing suction filtration to obtain the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel, which is abbreviated as Cell-g-P (NIPAm-co-MA) nanofiber hydrogel.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4And (3) preparing the magnetic nanofiber composite hydrogel.
0.3g of Cell-g-P (NIPAm-co-MA) hydrogel is soaked in 100mL of ferrous chloride (0.0852g) and ferric chloride (0.2316g) solution, 10mL of 1mol/L ammonia water is added, and reaction is carried out for 6h to obtain the Cell-g-P (NIPAm-co-MA)/Fe3O4The magnetic nanofiber composite hydrogel is temperature-sensitive hydrogel for copper ion adsorption.
Cell-g-P(NIPAm-co-MA)/Fe3O4The diameter of the fiber in the magnetic nano-fiber composite hydrogel is 170 +/-70 nm, and the porosity and the specific surface area of the hydrogel are 91.8 percent and 26.1m respectively2(ii)/g, magnetization of 0.024 emu/g. Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic nanofiber composite hydrogel pair Cu2+The saturated adsorption amount of (A) was 410.1 mg/g.
Example 3
1) Preparation of cellulose nanofibers
3g of tetrahydrofuran and 7g N, N' -dimethylformamide were added to a serum bottle, and then 0.3g of cellulose acetate was added and dissolved with stirring to form a clear and transparent solution. The solution was poured into a petri dish and frozen in a freezer at-20 ℃ for 3 h. After the reaction is finished, the mixture is taken out and put into an ice-water mixture, and distilled water is replaced every 6 hours for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.15mol/L NaOH/ethanol solution for 24h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) And (3) preparing the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel.
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
Dissolving 0.5g N-isopropyl acrylamide, 0.25g maleic anhydride and 0.008g N, N' -methylene bisacrylamide in 15mL of 1mol/L nitric acid solution to obtain reaction liquid A; dissolving 0.2g of ammonium ceric nitrate in 15mL of 1mol/L nitric acid solution, and adding 0.5g of cellulose nanofiber and 0.05g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting for 3 hours at the reaction temperature of 40 ℃, washing with distilled water, performing Soxhlet extraction with acetone, and performing suction filtration to obtain the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel, which is abbreviated as Cell-g-P (NIPAm-co-MA) nanofiber hydrogel.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4And (3) preparing the magnetic nanofiber composite hydrogel.
0.4g of Cell-g-P (NIPAm-co-MA) hydrogel is soaked in 100mL of ferrous chloride (0.0852g) and ferric chloride (0.2316g) solution, 10mL of 1mol/L ammonia water is added, and reaction is carried out for 6h to obtain the Cell-g-P (NIPAm-co-MA)/Fe3O4The magnetic nanofiber composite hydrogel is temperature-sensitive hydrogel for copper ion adsorption.
Cell-g-P(NIPAm-co-MA)/Fe3O4The diameter of the fiber in the magnetic nano-fiber composite hydrogel is 189 +/-90 nm, and the porosity and the specific surface area of the hydrogel are 92.1 percent and 23.1 percent respectivelym2(ii) a magnetization of 0.020 emu/g. Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic nanofiber composite hydrogel pair Cu2+The saturated adsorption amount of (A) was 380.1 mg/g.
Example 4
1) Preparation of cellulose nanofibers
2g tetrahydrofuran and 8g N, N' -dimethylformamide were added to a serum bottle, and then 0.45g cellulose acetate was added and dissolved with stirring to form a clear and transparent solution. The solution was poured into a petri dish and frozen in a freezer at-15 ℃ for 3 h. After the reaction is finished, the mixture is taken out and put into an ice-water mixture, and distilled water is replaced every 6 hours for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.2mol/L NaOH/ethanol solution for 24h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) And (3) preparing the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel.
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
Dissolving 0.7g N-isopropyl acrylamide, 0.2g maleic anhydride and 0.005g N, N' -methylene bisacrylamide in 15mL nitric acid solution of 1mol/L to obtain reaction liquid A; dissolving 0.2g of ammonium ceric nitrate in 15mL of 1mol/L nitric acid solution, and adding 0.4g of cellulose nanofiber and 0.02g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting for 4 hours at the reaction temperature of 40 ℃, washing with distilled water, performing Soxhlet extraction with acetone, and performing suction filtration to obtain the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride) hydrogel, which is abbreviated as Cell-g-P (NIPAm-co-MA) nanofiber hydrogel.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4And (3) preparing the magnetic nanofiber composite hydrogel.
0.2g of Cell-g-P (NIPAm-co-MA) hydrogel is soaked in 100mL of ferrous chloride (0.0852g) and ferric chloride (0.2316g) solution, 10mL of 1mol/L ammonia water is added, and reaction is carried out for 8h to obtain Cell-g-P (NIPAm-co-MA)/Fe3O4The magnetic nanofiber composite hydrogel is temperature-sensitive hydrogel for copper ion adsorption.
Cell-g-P(NIPAm-co-MA)/Fe3O4The diameter of the fiber in the magnetic nano-fiber composite hydrogel is 169 +/-80 nm, and the porosity and the specific surface area of the hydrogel are 93.2 percent and 22.1m respectively2(ii)/g, and a magnetization of 0.025 emu/g. Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic nanofiber composite hydrogel pair Cu2+The saturated adsorption amount of (A) was 397.1 mg/g.
Comparative example 1
The difference from the embodiment 1 is that: step 1) dissolving cellulose acetate in a mixed solvent of tetrahydrofuran and N, N' -dimethylformamide, and preparing a cellulose casting film by adopting a casting film forming method.
The subsequent steps are the same as example 1, and the cellulose cast film grafted poly (N-isopropylacrylamide-co-maleic anhydride)/Fe is finally obtained3O4Magnetic composite hydrogel. The hydrogel had a porosity and a specific surface area of 60.3% and 1.19m, respectively2(ii) in terms of/g. Compared with fiber membrane hydrogel, the porosity and specific surface area are greatly reduced. Mainly because the porous structure cannot be formed like a fiber membrane hydrogel. Cast film hydrogel to Cu2+Has a saturated adsorption capacity of 120.1m2/g。
Comparative example 2
The difference from the embodiment 1 is that: the addition amount of the vinyl-modified silica in the step 2) is 0. Finally obtaining the cellulose nano-fiber grafted poly (N-isopropyl acrylamide-co-maleic anhydride)/Fe3O4Magnetic composite hydrogel.
Cellulose nanofiber grafted poly (N-isopropylacrylamide-co-maleic anhydride)/Fe3O4The diameter of the fiber in the magnetic composite hydrogel is 161 +/-55 nm. The porosity and the specific surface area were 81.1% and 15.12m, respectively2(ii) in terms of/g. Fibrous hydrogel to Cu2+The saturated adsorption amount of (A) was 267.78 mg/g. The main purpose of adding the vinyl modified silica into the reaction system is to improve the porosity and the specific surface area of the hydrogel and further improve the heavy metal adsorption capacity of the hydrogel.
Comparative example 3
The difference from the embodiment 1 is that: the amount of maleic anhydride added in step 2) was 0. Finally obtaining the cellulose nanofiber grafted poly (N-isopropyl acrylamide) hydrogel. The diameter of the fiber in the hydrogel is 151 +/-78 nm, and the porosity and the specific surface area of the hydrogel are 67.2 percent and 0.45m respectively2(ii) in terms of/g. The hydrogel is aligned with Cu2+The saturated adsorption amount of (A) was 110.6 mg/g.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. The preparation method of the temperature-sensitive hydrogel is characterized by comprising the following steps:
preparing cellulose acetate nanofibers;
deacetylating the cellulose acetate nano-fibers by using alkali liquor to obtain cellulose nano-fibers;
preparation of cellulose nanofiber graft poly(s) using the cellulose nanofibersN-isopropylacrylamide-co-maleic anhydride) hydrogel;
grafting the cellulose nanofibers with poly (A)N-Isopropyl acrylamide-coSoaking maleic anhydride hydrogel in a mixed solution of ferrous chloride and ferric chloride, adding ammonia water for reaction to obtain cellulose nanofiber graft poly (A) (B)N-Isopropyl acrylamide-co-maleic anhydride)/Fe3O4Magnetic nanofiber composite hydrogel, namely the temperature-sensitive hydrogel;
the cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-maleic anhydride) hydrogel is prepared by the following method:
will be provided withN-isopropylacrylamide, maleic anhydride,N, N’Dissolving methylene bisacrylamide in a nitric acid solution to obtain a reaction solution A;
dissolving ammonium ceric nitrate in a nitric acid solution, and adding vinyl modified silicon dioxide and the cellulose nanofiber to obtain a reaction solution B;
dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at 30-60 ℃, sequentially washing with distilled water, performing Soxhlet extraction with acetone, and performing suction filtration to obtain the cellulose nanofiber graft polymer (A)N-Isopropyl acrylamide-co-maleic anhydride) hydrogel;
the preparation method of the cellulose acetate nanofiber comprises the following steps:
dissolving cellulose acetate in tetrahydrofuran andN,N’quenching the quenching liquid at-30 to-15 ℃, washing with distilled water to remove tetrahydrofuran and dimethylformamideN,N’-dimethylformamide, cellulose acetate nanofibres obtained by freeze drying;
the alkali liquor is an ethanol solution of NaOH, wherein the concentration of the NaOH is 0.1-0.2 mol/L;
in the reaction solution a:N-isopropylacrylamide, maleic anhydride,N, N’The weight parts of the methylene bisacrylamide are respectively 5-10 parts, 2-3 parts and 0.05-0.1 part; in the reaction solution B: 1-3 parts of ammonium ceric nitrate, 2-6 parts of cellulose nanofiber and 0.2-0.5 part of vinyl modified silicon dioxide by weight;
the preparation method of the vinyl modified silicon dioxide comprises the following steps: reacting the vinyltriethoxysilane with silicon dioxide to obtain the vinyl modified silicon dioxide.
2. The method for producing a temperature-sensitive hydrogel according to claim 1, wherein in the quenching liquid, cellulose acetate, tetrahydrofuran andN,N’the weight parts of the-dimethylformamide are respectively 0.2-0.5 part, 1-3 parts and 5-10 parts.
3. The method for producing a temperature-sensitive hydrogel according to claim 1, wherein the molar ratio of ferrous chloride to ferric chloride in the mixed solution of ferrous chloride and ferric chloride is 1: 2; the concentration of the ammonia water is 1 mol/L.
4. Use of the temperature-sensitive hydrogel obtained by the preparation method of any one of claims 1 to 3 in heavy metal ion adsorption.
5. Use according to claim 4, wherein the heavy metal ions are copper ions.
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