CN110694593A - Preparation method of cyclodextrin adsorption material - Google Patents
Preparation method of cyclodextrin adsorption material Download PDFInfo
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- CN110694593A CN110694593A CN201911140506.1A CN201911140506A CN110694593A CN 110694593 A CN110694593 A CN 110694593A CN 201911140506 A CN201911140506 A CN 201911140506A CN 110694593 A CN110694593 A CN 110694593A
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Abstract
The invention discloses a preparation method of a cyclodextrin adsorption material, which comprises the following steps: step one, uniformly mixing beta-cyclodextrin, 4' -difluorobenzophenone and potassium carbonate to obtain a mixture, then putting the mixture and an organic solvent into a reaction vessel together, and stirring, heating and refluxing under the protection of inert gas; and step two, cooling after the reaction is finished, adding an ethanol/water solution (V/V =1: 1) with the same volume as the organic solvent, centrifuging, removing the supernatant, repeating the step until the supernatant is colorless, and drying the lower-layer solid-phase substance in vacuum to obtain the beta-cyclodextrin adsorption material. The reaction of the beta-cyclodextrin and the 4, 4' -difluorobenzophenone realizes the insoluble conversion of the beta-cyclodextrin, the whole reaction condition is relatively mild, hydrogen, high pressure, noble metal catalysts and the like are not needed, the process operation is convenient, the process is simple, the cost is low, and the method is an environment-friendly adsorption material preparation method.
Description
Technical Field
The invention relates to the technical field of adsorption materials, and particularly relates to a preparation method of a cyclodextrin adsorption material.
Background
Environmental pollution, particularly deterioration of water environment quality, is an important problem restricting the development of human society, and one of important technologies for treating polluted water quality is an adsorption method, so that development of an adsorption material which is environment-friendly and has an excellent effect becomes a focus of attention of many researchers. At present, among various adsorbing materials, the beta-cyclodextrin has the advantages of simple preparation method, low cost and unique molecular structure, and is a very potential adsorbing material. However, beta-cyclodextrin has good solubility in water, is difficult to recover when being applied to water resource treatment, and needs to be further modified to expand the physicochemical property of the beta-cyclodextrin. The beta-cyclodextrin is modified mainly by being immobilized on organic high molecular materials such as polyvinylamine, polyvinyl alcohol and the like and inorganic materials; is immobilized on insoluble natural polymer material such as chitosan, biochar, etc.; coupling polymerization is carried out with aromatic organic matters to form insoluble macromolecules.
Chinese patents CN108727600A, CN108554387A and CN108404878A propose that β -cyclodextrin can react with tetrafluoroterephthalonitrile to prepare insoluble cyclodextrin polymer material with excellent adsorption performance. The reaction of beta-cyclodextrin with 4, 4' -difluorodiphenyl sulfone to prepare the adsorbent material has also been reported in the literature. However, the tetrafluoroterephthalonitrile and 4, 4' -difluorodiphenylsulfone used in these two methods are expensive, toxic, and the use of them is limited by the high cost and potential post-treatment toxicity.
The invention provides a novel method for preparing cyclodextrin polymer, which is characterized in that beta-cyclodextrin and 4,4 '-difluorobenzophenone are subjected to polymerization reaction to prepare a water-insoluble beta-cyclodextrin adsorption material, the preparation process is simple and environment-friendly, the used 4, 4' -difluorobenzophenone is low in toxicity, and the way for preparing the beta-cyclodextrin insoluble adsorption material is widened.
Disclosure of Invention
The invention provides a preparation method of a cyclodextrin adsorption material with simple process, environmental friendliness and low toxicity.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a cyclodextrin adsorption material comprises the following steps:
step one, uniformly mixing beta-cyclodextrin, 4' -difluorobenzophenone and potassium carbonate to obtain a mixture, then putting the mixture and an organic solvent into a reaction vessel together, and stirring, heating and refluxing under the protection of inert gas;
and step two, cooling after the reaction is finished, adding an ethanol/water solution (V/V =1: 1) with the same volume as the organic solvent, centrifuging, removing the supernatant, repeating the step until the supernatant is colorless, and drying the lower-layer solid-phase substance in vacuum to obtain the beta-cyclodextrin adsorption material.
Preferably, the organic solvent may be one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and ethylene glycol;
preferably, the mole fractions of β -cyclodextrin, 4' -difluorobenzophenone, and potassium carbonate in the mixture are 5% ~ 20, 10% ~ 30, 30% ~ 70, respectively;
preferably, the ratio of the volume of the organic solvent (mL) to the sum of the masses of beta-cyclodextrin and 4, 4' -difluorobenzophenone (g) is (3 ~ 10): 1;
preferably, the inert gas is one of nitrogen, helium and argon;
preferably, the heating reflux temperature is 80 ~ 160 ℃, and the heating reflux reaction time is 2 ~ 20 h;
preferably, the vacuum drying condition is-0.1 MPa, 50 ~ 80 ℃ and 12 h.
Compared with the prior art, the invention has the following beneficial effects:
the reaction of the beta-cyclodextrin and the 4, 4' -difluorobenzophenone realizes the insoluble conversion of the beta-cyclodextrin, the whole reaction condition is relatively mild, hydrogen, high pressure, noble metal catalysts and the like are not needed, the process operation is convenient, the process is simple, the cost is low, and the method is an environment-friendly adsorption material preparation method.
Drawings
FIG. 1 is a picture of the appearance of a sample of example 1 of the present invention.
Fig. 2 is a fourier transform infrared spectrum of the cyclodextrin adsorbing material prepared in example 1 of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1
The preparation method of the cyclodextrin adsorption material in the embodiment comprises the following steps:
step one, taking 11.0 g, 4.2 g and 9.3g of beta-cyclodextrin (98%, AR), 4 '-difluorobenzophenone (99%, AR) and potassium carbonate (99%, AR) respectively according to the proportion that the mole fractions of the beta-cyclodextrin, the 4, 4' -difluorobenzophenone and the potassium carbonate are 10%, 20% and 70%, and uniformly mixing to obtain a mixture; according to the ratio of the volume (mL) of the organic solvent to the sum (g) of the mass of the beta-cyclodextrin and the mass of the 4, 4' -difluorobenzophenone being 6:1, 91.2 mL of N, N-dimethylacetamide is taken; putting the mixture and an organic solvent into a round bottom three-neck flask with a magnetic stirrer, connecting the flask with a serpentine condenser pipe and a nitrogen inlet, heating in an oil bath at 120 ℃, and carrying out reflux reaction for 12 hours;
and step two, cooling, adding 91.2 mL of ethanol/water solution, centrifuging, removing supernatant, repeating for 3 times, drying the solid-phase substance at-0.1 MPa and 60 ℃ for 12 hours to obtain a product in a light yellow powder shape (shown in figure 1), recording the product quality, and detecting the adsorption performance.
The product mass is 10.6 g, and the methylene blue adsorption value is 211 mg/g.
Example 2
The preparation method of the cyclodextrin adsorption material in this embodiment includes the following steps:
step one, taking the beta-cyclodextrin (98 percent, AR), the 4,4 ' -difluorobenzophenone with the purity of 99 percent (99 percent, AR) and the potassium carbonate (99 percent, AR) according to the proportion that the mole fractions of the beta-cyclodextrin, the 4,4 ' -difluorobenzophenone and the potassium carbonate are 20 percent, 20 percent and 60 percent, and uniformly mixing the beta-cyclodextrin, the 4,4 ' -difluorobenzophenone and the potassium carbonate to obtain a mixture, wherein the weight percentages of the beta-cyclodextrin, the AR and the potassium carbonate are respectively 22.0g, 4.2 g and 8.0 g; taking 78.6 mL of N, N-dimethylacetamide according to the ratio of the volume (mL) of the organic solvent to the sum (g) of the mass of the beta-cyclodextrin and the mass of the 4, 4' -difluorobenzophenone being 3: 1; putting the mixture and an organic solvent into a round bottom three-neck flask with a magnetic stirrer, connecting the flask with a serpentine condenser pipe and a helium inlet, heating in an oil bath at 140 ℃, and carrying out reflux reaction for 15 hours;
and step two, cooling, adding 78.6 mL of ethanol/water solution, centrifuging, removing supernatant, repeating for 3 times, drying the solid-phase substance at-0.1 MPa at 70 ℃ for 12 hours to obtain a product in a light yellow powder shape, recording the product quality, and detecting the adsorption performance.
The product mass is 12.1 g, and the methylene blue adsorption value is 207 mg/g.
Example 3
The preparation method of the cyclodextrin adsorption material in this embodiment includes the following steps:
taking 10.0 g, 3.8 g and 4.5g of beta-cyclodextrin (98%, AR), 4 '-difluorobenzophenone (99%, AR) and potassium carbonate (99%, AR) respectively according to the proportion that the mole fractions of the beta-cyclodextrin, the 4, 4' -difluorobenzophenone and the potassium carbonate are 15%, 30% and 55%, and uniformly mixing to obtain a mixture; taking 55.2 mL of N, N-dimethylacetamide according to the ratio of the volume (mL) of the organic solvent to the sum (g) of the mass of the beta-cyclodextrin and the mass of the 4, 4' -difluorobenzophenone being 4: 1; putting the mixture and an organic solvent into a round-bottom three-neck flask with a magnetic stirrer, connecting a serpentine condenser pipe and an argon inlet on the flask, heating the flask in an oil bath at 130 ℃, and carrying out reflux reaction for 18 hours.
And step two, cooling, adding 55.2 mL of ethanol/water solution, centrifuging, removing supernatant, repeating for 4 times, drying the solid-phase substance at-0.1 MPa at 80 ℃ for 12 hours to obtain a product in a light yellow powder shape, recording the product quality, and detecting the adsorption performance.
The product mass is 7.3 g, and the methylene blue adsorption value is 193 mg/g.
Example 4
The preparation method of the cyclodextrin adsorption material in this embodiment includes the following steps:
according to the proportion that the mole fractions of beta-cyclodextrin, 4 '-difluorobenzophenone and potassium carbonate are 15%, 35% and 50%, respectively taking 11.2 g, 5.0 g and 4.5g of beta-cyclodextrin (98%, AR), 4' -difluorobenzophenone (99%, AR) and potassium carbonate (99%, AR) and uniformly mixing to obtain a mixture; taking 64.8 mL of N, N-dimethylacetamide according to the ratio of the volume (mL) of the organic solvent to the sum (g) of the mass of the beta-cyclodextrin and the mass of the 4, 4' -difluorobenzophenone being 4: 1; putting the mixture and an organic solvent into a round bottom three-neck flask with a magnetic stirrer, connecting a serpentine condenser pipe and an argon inlet on the flask, heating the flask in 100 ℃ oil bath, and carrying out reflux reaction for 20 hours.
And step two, cooling, adding 64.8 mL of ethanol/water solution, centrifuging, removing supernatant, repeating for 3 times, drying the solid-phase substance at-0.1 MPa at 60 ℃ for 12 hours to obtain a product in a light yellow powder shape, recording the product quality, and detecting the adsorption performance.
The product mass is 10.6 g, and the methylene blue adsorption value is 174 mg/g.
The invention relates to the detection of the adsorption capacity, which takes methylene blue adsorption value (reference standard GB/T12496.1 ~ 12496.22-1999) as a standard.
The functional group characteristics of the beta-cyclodextrin adsorbing material prepared by the invention are shown in figure 2. 3400 cm-1The broad peak at the position represents the O-H bond in the beta-cyclodextrin molecule, 2930 cm-1Is due to the symmetric and asymmetric stretching vibration peaks of C-H. 1595 cm-1The peak is caused by vibration of benzene ring skeleton in 4, 4' -difluorobenzophenone, 1256 cm-1The absorption peak is aromatic ether bond in the reaction product of beta-cyclodextrin and 4, 4' -difluorobenzophenone, and the cyclodextrin is 1154 cm-1,1080 cm-1,1039 cm-1And 955 cm-1The absorption peaks are respectively a C-2/C-3 stretching vibration peak in a hexatomic ring of cyclodextrin, a C-O-C stretching vibration peak of a glucopyranose unit, a C-O stretching vibration peak and a C-H stretching vibration peak of C-6. The infrared spectrogram proves that the reaction product simultaneously contains the beta-cyclodextrin and the 4,4 '-difluorobenzophenone, and the beta-cyclodextrin and the 4, 4' -difluorobenzophenone are reacted.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and other modifications or equivalent substitutions made by the technical solution of the present invention by the ordinary skilled in the art should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the cyclodextrin adsorption material is characterized by comprising the following steps:
step one, uniformly mixing beta-cyclodextrin, 4' -difluorobenzophenone and potassium carbonate to obtain a mixture, then putting the mixture and an organic solvent into a reaction vessel together, and stirring, heating and refluxing under the protection of inert gas;
and step two, cooling after the reaction is finished, adding an ethanol/water solution (V/V =1: 1) with the same volume as the organic solvent, centrifuging, removing the supernatant, repeating the step until the supernatant is colorless, and drying the lower-layer solid-phase substance in vacuum to obtain the beta-cyclodextrin adsorption material.
2. The method for preparing cyclodextrin adsorption material of claim 1, wherein the organic solvent is one selected from N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and ethylene glycol.
3. The method for preparing cyclodextrin adsorbing material according to claim 1, wherein the mole fractions of β -cyclodextrin, 4' -difluorobenzophenone and potassium carbonate in the mixture are 5% ~ 20, 10% ~ 30 and 30% ~ 70 respectively.
4. The method of preparing a cyclodextrin adsorption material of claim 1, wherein the ratio of the volume of organic solvent (mL) to the sum of the mass of β -cyclodextrin and 4, 4' -difluorobenzophenone (g) is (3 ~ 10): 1.
5. The method of claim 1, wherein the inert gas is one of nitrogen, helium and argon.
6. The preparation method of cyclodextrin adsorption material of claim 1, wherein the heating reflux temperature is 80 ~ 160 ℃, and the heating reflux reaction time is 2 ~ 20 h.
7. The method for preparing cyclodextrin adsorption material of claim 1, wherein the vacuum drying condition is-0.1 MPa, 50 ~ 80 ℃, 12 h.
8. A product obtained by the method of making a cyclodextrin adsorptive material of any one of claims 1 ~ 7.
9. Use of a cyclodextrin-adsorbing material of any of claims 1 ~ 7, for the preparation of a material for the conversion of beta-cyclodextrin to insoluble beta-cyclodextrin-adsorbing material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113842897A (en) * | 2021-10-23 | 2021-12-28 | 河南农业大学 | Preparation method of cyclodextrin polymer for adsorbing organic dye |
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| US20040028901A1 (en) * | 2002-02-25 | 2004-02-12 | Rumpf Frederick H. | Compositions comprising continuous networks and monoliths |
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Cited By (2)
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| CN113842897A (en) * | 2021-10-23 | 2021-12-28 | 河南农业大学 | Preparation method of cyclodextrin polymer for adsorbing organic dye |
| CN113842897B (en) * | 2021-10-23 | 2024-01-09 | 河南农业大学 | Preparation method of cyclodextrin polymer for adsorbing organic dye |
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