CN114471480A - Method for preparing chitosan-based adsorbent based on click chemical reaction - Google Patents
Method for preparing chitosan-based adsorbent based on click chemical reaction Download PDFInfo
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- CN114471480A CN114471480A CN202210200534.3A CN202210200534A CN114471480A CN 114471480 A CN114471480 A CN 114471480A CN 202210200534 A CN202210200534 A CN 202210200534A CN 114471480 A CN114471480 A CN 114471480A
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a chitosan-based adsorbent based on a click chemical reaction. The method comprises the following steps: obtaining the sulfhydrylated kaolin; mixing the sulfhydrylation kaolin, the compound containing olefine aldehyde group, the catalyst and the first organic solvent to obtain a liquid phase mixture; carrying out ultraviolet irradiation on the liquid phase mixture, and removing the organic solvent and the residual compound containing olefine aldehyde groups to obtain the aldehyde kaolin; mixing the aldehyde kaolin, the chitosan and a second organic solvent, and carrying out Schiff base reaction to obtain the chitosan-based adsorbent. When the chitosan-based adsorbent is used for adsorption, due to the introduction of the amino matrix, functional groups of the adsorbent for adsorbing pollutants are not consumed, and a sulfhydryl group is introduced, so that the adsorption capacity of the adsorbent is improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a chitosan-based adsorbent based on a click chemical reaction.
Background
A large number of amino and hydroxyl functional groups exist on chitosan molecules, and the main characteristic of the functional group sites is to chelate heavy metal ions, so that the chitosan has a good adsorption effect on most heavy metal ions. And the two can produce various derivatives with different structures and different properties through reactions such as acylation, carboxylation, etherification, alkylation, grafting, crosslinking and the like, so the chitosan has great attention in the field of adsorption.
The preparation of novel adsorbents by combining inorganic adsorbents with chitosan has become a research focus nowadays, for example, chitosan and kaolin are combined together through a crosslinking reaction, but the crosslinking reaction consumes functional groups (amino and hydroxyl) in the chitosan structure for adsorbing pollutants, so that the high adsorption capacity of chitosan cannot be utilized to the maximum extent. Therefore, it is a problem to be solved to develop a binding method that does not consume a functional group that adsorbs a contaminant.
Disclosure of Invention
The application provides a method for preparing a chitosan-based adsorbent based on a click chemistry reaction, and the adsorbent without consuming functional groups for adsorption is prepared.
The present application provides a method for preparing a chitosan-based adsorbent based on a click chemistry reaction, the method comprising the steps of:
obtaining the sulfhydrylated kaolin;
mixing the sulfhydrylation kaolin, the compound containing olefine aldehyde group, the catalyst and the first organic solvent to obtain a liquid phase mixture;
carrying out ultraviolet irradiation on the liquid phase mixture, and removing the organic solvent and the residual compound containing olefine aldehyde groups to obtain the aldehyde kaolin;
mixing the aldehyde kaolin, the chitosan and a second organic solvent, and carrying out Schiff base reaction to obtain the chitosan-based adsorbent.
Optionally, the compound containing an enal group includes at least one of 2-ethylacrolein and crotonaldehyde.
Optionally, the catalyst comprises any one of dihydroxymethylpropionic acid, benzoin dicarbaldehyde and benzaldehyde.
Optionally, the first organic solvent includes any one of tetrahydrofuran, cyclohexane, cyclohexanone and toluene cyclohexanone.
Optionally, the second organic solvent includes any one of acetic acid solution, formic acid and methyl acetate.
Optionally, the method for preparing the chitosan-based adsorbent comprises the steps of mixing the aldehyde kaolin, chitosan and a second organic solvent, and performing schiff base reaction, wherein the step of preparing the chitosan-based adsorbent specifically comprises the following steps:
mixing chitosan and a second organic solvent to obtain a chitosan solution;
and mixing the chitosan solution with the aldehyde kaolin, and stirring to perform Schiff base reaction to obtain the chitosan-based adsorbent.
Optionally, the temperature of the Schiff base reaction is 25-40 ℃, and the time of the Schiff base reaction is 4-5 hours.
Optionally, the obtained thiolated kaolin specifically includes:
mixing ethanol, pure water, ammonia water and 3-mercaptopropyltriethoxysilane, and carrying out water bath reaction to obtain a mixed solution;
and mixing the mixed solution with kaolin, placing the mixture in a protective atmosphere for a first reaction, and purifying to obtain the sulfhydrylated kaolin.
Optionally, the temperature of the water bath reaction is 60-65 ℃, and the time of the water bath reaction is 1-3 h.
Optionally, the purification comprises washing, centrifugation and vacuum drying.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the method provided by the embodiment of the application, the aldehydized kaolin is obtained by sulfhydrylation kaolin; introducing chitosan to perform Schiff base reaction to obtain a chitosan-based adsorbent; when the chitosan-based adsorbent is used for adsorption, due to the introduction of the amino matrix, functional groups of the adsorbent for adsorbing pollutants are not consumed, and a sulfhydryl group is introduced, so that the adsorption capacity of the adsorbent is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a schematic flow chart of a method for preparing a chitosan-based adsorbent based on a click chemistry reaction according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a reaction technique route of chitosan-based adsorbent provided in the examples of the present application;
FIG. 3 is a graph showing the adsorption amount of copper ions by the adsorbents in the examples and comparative examples at different pH values.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. For example, the room temperature may be a temperature within a range of 10 to 35 ℃.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a method for preparing a chitosan-based adsorbent based on a click chemistry reaction, as shown in fig. 1, the method including the steps of:
s1, obtaining sulfhydrylation kaolin;
s2, mixing the sulfhydrylation kaolin, the compound containing the olefine aldehyde group, the catalyst and a first organic solvent to obtain a liquid phase mixture;
s3, carrying out ultraviolet irradiation on the liquid phase mixture, and removing the organic solvent and the residual compound containing the olefine aldehyde group to obtain aldehyde kaolin;
and S4, mixing the aldehyde kaolin, the chitosan and a second organic solvent, and carrying out Schiff base reaction to obtain the chitosan-based adsorbent.
Specifically, CS is chitosan GL, kaolin AGL, and TGL are kaolin thiolated, and by mixing AGL with CS, the aldehyde groups on AGL and the amino groups on chitosan can undergo schiff base reaction. Because of the introduction of sulfur atoms, the sulfur atoms can carry out chelation with heavy metal ions, thereby improving the adsorption capacity of the adsorbent.
In some embodiments, the enal group-containing compound includes at least one of 2-ethylacrolein and crotonaldehyde.
The reason for selecting 2-ethylacrolein and crotonaldehyde is that the two materials have double bonds which can react with sulfydryl, and the positive effect of enabling the click chemistry reaction to be rapidly and efficiently carried out is achieved.
In some embodiments, the catalyst comprises any one of dihydroxymethylpropionic acid, benzoin dicarboxaldehyde, and benzaldehyde.
Specifically, the dihydroxymethylpropanoic acid and the like are used as catalysts to catalyze the ultraviolet light to catalyze the sulfydryl and the double bond in click chemistry, so that free radical addition reaction is carried out on the sulfydryl and the double bond, and the positive effect of successful occurrence of click chemistry reaction is achieved.
In some embodiments, the first organic solvent comprises any one of tetrahydrofuran, cyclohexane, cyclohexanone, and toluene cyclohexanone.
The reason why the first organic solvent is selected from tetrahydrofuran, cyclohexane, cyclohexanone and toluene cyclohexanone is based on the principle of similarity and compatibility, and if other non-organic solvents such as water are selected, the adverse effects that organic matters cannot be dissolved and the reaction cannot be carried out are caused.
In some embodiments, the second organic solvent comprises any one of acetic acid solution, formic acid, and methyl acetate.
The reason for selecting the second organic solvent to dissolve the chitosan for the reaction is that the chitosan is difficult to dissolve in most organic solvents, water and alkali, and if the chitosan is not dissolved by the second organic solvent, the chitosan is difficult to dissolve, and the subsequent reaction cannot be carried out.
In some embodiments, the mixing of the aldehydic kaolin, the chitosan and the second organic solvent, and performing schiff base reaction to obtain the chitosan-based adsorbent specifically includes:
mixing chitosan and a second organic solvent to obtain a chitosan solution;
and mixing the chitosan solution with the aldehyde kaolin, and stirring to perform Schiff base reaction to obtain the chitosan-based adsorbent.
Specifically, the chitosan and the second organic solvent are mixed, and then the chitosan solution is mixed with the aldehyde kaolin, so that the utilization degree of the chitosan base can be improved, the raw materials can be saved, and the yield can be improved.
In some embodiments, the temperature of the schiff base reaction is 25 to 40 ℃ and the time of the schiff base reaction is 4 to 5 hours.
The reason for controlling the temperature of the Schiff base reaction is that the temperature of the Schiff base reaction conditions should not be too high, and if the temperature is not in the above range, the Schiff base is unstable at high temperature, which is an adverse effect.
In some embodiments, the obtaining of a thiolated kaolin, specifically includes:
mixing ethanol, pure water, ammonia water and 3-mercaptopropyltriethoxysilane, and carrying out water bath reaction to obtain a mixed solution;
and mixing the mixed solution with kaolin, placing the mixture in a protective atmosphere for a first reaction, and purifying to obtain the sulfhydrylated kaolin.
The ethanol, the pure water, the ammonia water and the 3-mercaptopropyltriethoxysilane are selected because the positive effect of preparing for the successful occurrence of the subsequent click chemical reaction is achieved in order to introduce the sulfydryl, and the reason of placing in the protective atmosphere is to avoid the material from being oxidized to influence the experimental effect, and the protective atmosphere can be a nitrogen protective atmosphere or an inert gas protective atmosphere.
In some embodiments, the temperature of the water bath reaction is 60-65 ℃ and the time of the water bath reaction is 1-3 h.
The reason for controlling the temperature of the water bath reaction to be 60-65 ℃ is that the reaction needs to be carried out at a certain temperature, which has the positive effect of improving the reaction efficiency, and for example, the adverse effect that the reaction cannot be carried out or is insufficient due to the temperature being out of the above range can be caused.
In some embodiments, the purification comprises washing, centrifugation, and vacuum drying.
The purification process of obtaining mercaptolated kaolin is characterized in that the purity of the mercaptolated kaolin can reach more than 90 percent through solid-liquid separation, vacuum drying to remove water, washing, centrifugation and vacuum drying.
The process of the present invention will be described in detail below with reference to examples, comparative examples and experimental data.
Examples
This example provides a method for preparing a novel chitosan-based adsorbent using thiol-olefin click chemistry, the method comprising:
s1, obtaining sulfhydrylation kaolin;
s2, mixing the sulfhydrylation kaolin, the compound containing the olefine aldehyde group, the catalyst and a first organic solvent to obtain a liquid phase mixture;
s3, carrying out ultraviolet irradiation on the liquid phase mixture, and removing the organic solvent and the residual compound containing the olefine aldehyde group to obtain aldehyde kaolin;
and S4, mixing the aldehyde kaolin, the chitosan and a second organic solvent, and carrying out Schiff base reaction to obtain the chitosan-based adsorbent.
The reaction technical scheme is shown in fig. 2, which shows the process that amino in chitosan is utilized to produce chitosan-based adsorbent which is not easy to be consumed. The method specifically comprises the following steps: sulfhydrylated kaolin: accurately measuring 59.5ml of absolute ethyl alcohol and 10.5ml of ultrapure water into a 100ml three-neck flask, adding 600 mu l of ammonia water and 0.42g of MPTMS (3-mercaptopropyltriethoxysilane), carrying out water bath reaction for 3h at 65 ℃, taking out and standing for 15min after the reaction is finished, then slowly adding 1g of kaolin under vigorous stirring, stirring for 6h under a nitrogen atmosphere at room temperature, after the reaction is finished, alternately washing for 3 times by using ethyl alcohol and ultrapure water, centrifuging, and carrying out vacuum drying for 10h at 80 ℃ to obtain the sulfhydrylation modified kaolin (TGL).
Thiolated kaolin complexed with chitosan (GL-CS): to prepare AGL, TGL (0.6g), 2-ethylacrolein (0.3g) and dimethylolpropionic acid (0.02g) were dissolved in 20ml of THF, and the mixture was irradiated under a UV lamp for 0.5 hour. After removal of THF, AGL was obtained by washing with methanol to remove unreacted 2-ethylacrolein. To synthesize GL-CS, 0.3g of chitosan was dispersed in 20ml of acetic acid solution (2%), AGL (1.0g) was then added under vigorous stirring, and after stirring at 40 ℃ for 5 hours, washing was repeated with distilled water and ethanol, suction filtration under reduced pressure, and freeze-drying for 12 hours gave GL-CS.
Comparative example 1
This comparative example differs from the examples in that: and (3) performing crosslinking reaction combination on the chitosan and the kaolin to obtain the adsorbent.
Effect detection
The experimental steps are as follows: two materials were prepared: the adsorbent bonded by the cross-linking reaction of the chitosan/kaolin of the comparative example is a; in the embodiment, the chitosan-based adsorbent formed by combining chitosan and kaolin through a click chemical reaction is B; the pH of the solution was set to a range of 3.0-7.0, and the Pb2+ solution was first adjusted to pH 2.0, 3.0, 4.0, 5.0, 6.0, and 7.0 with 0.1mol/L HAC and NaOH for further use. Then 0.05g of material A and material B were weighed into a 250mL Erlenmeyer flask, 100m of 120mg/l Pb2+ solution with different pH was added to the Erlenmeyer flask, and the Erlenmeyer flask was placed in a constant temperature shaker at 120rpm and 25 ℃ for 24 h. Then, the supernatant in the Erlenmeyer flask was filtered through a 0.45 μm filter, and the absorbance of the supernatant was measured by a flame atomic spectrophotometer to calculate the residual concentration and the amount of copper ions adsorbed in the solution.
qeIn order to balance the adsorption capacity, mg/g; c0Is the initial concentration of Pb2+, CeThe concentration of Pb2+ in the adsorbed solution is mg/l; m is the mass of the adsorbent, g; v is the volume of the solution, ml. The results of the tests are shown in table 1 and fig. 3.
Table 1.
As can be seen from table 1, when the amount of the adsorbent used in the examples was 0.05g, the adsorption rate was 64.55%, the maximum cycle number was 7, and the maximum adsorption amount was 11.54mg/g, and as can be seen from fig. 3, when the pH was 4, the adsorption amount of the material a was 11.54mg/g at the maximum, and the maximum adsorption amount of the material B reached 25.82 mg/g. Compared with a cross-linking reaction, the kaolin/chitosan adsorbent combined by the click chemical reaction obviously improves the adsorption performance, and is a novel adsorbent with a good prospect.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing a chitosan-based adsorbent based on a click chemistry reaction, comprising the steps of:
obtaining the sulfhydrylated kaolin;
mixing the sulfhydrylation kaolin, the compound containing olefine aldehyde group, the catalyst and the first organic solvent to obtain a liquid phase mixture;
carrying out ultraviolet irradiation on the liquid phase mixture, and removing the organic solvent and the residual compound containing olefine aldehyde groups to obtain the aldehyde kaolin;
mixing the aldehyde kaolin, the chitosan and a second organic solvent, and carrying out Schiff base reaction to obtain the chitosan-based adsorbent.
2. The method of claim 1, wherein the enal group-containing compound includes at least one of 2-ethylacrolein and crotonaldehyde.
3. The method of claim 1, wherein the catalyst comprises any one of dihydroxymethylpropionic acid, benzoin dicarboxaldehyde, and benzophenone.
4. The method of claim 1, wherein the first organic solvent comprises any one of tetrahydrofuran, cyclohexane, cyclohexanone, and toluene cyclohexanone.
5. The method of claim 1, wherein the second organic solvent comprises any one of an acetic acid solution, formic acid, and methyl acetate.
6. The method as claimed in claim 1, wherein the mixing of the aldehydized kaolin, the chitosan and the second organic solvent and the schiff base reaction are carried out to obtain the chitosan-based adsorbent, which specifically comprises:
mixing chitosan and a second organic solvent to obtain a chitosan solution;
and mixing the chitosan solution with the aldehyde kaolin, and stirring to perform Schiff base reaction to obtain the chitosan-based adsorbent.
7. The method according to claim 1, wherein the temperature of the schiff base reaction is 25-40 ℃ and the time of the schiff base reaction is 4-5 hours.
8. The method according to claim 1, wherein the obtaining of the thiolated kaolin comprises:
mixing ethanol, pure water, ammonia water and 3-mercaptopropyltriethoxysilane, and carrying out water bath reaction to obtain a mixed solution;
and mixing the mixed solution with kaolin, placing the mixture in a protective atmosphere for a first reaction, and purifying to obtain the sulfhydrylation kaolin.
9. The method as claimed in claim 1, wherein the temperature of the water bath reaction is 60-65 ℃ and the time of the water bath reaction is 1-3 h.
10. The method of claim 1, wherein the purifying comprises washing, centrifuging, and vacuum drying.
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