CN105273219A - Preparation method of porous cyclodextrin polymer - Google Patents
Preparation method of porous cyclodextrin polymer Download PDFInfo
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- CN105273219A CN105273219A CN201510674629.9A CN201510674629A CN105273219A CN 105273219 A CN105273219 A CN 105273219A CN 201510674629 A CN201510674629 A CN 201510674629A CN 105273219 A CN105273219 A CN 105273219A
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Abstract
The invention discloses a preparation method of a porous cyclodextrin polymer. The preparation method comprises steps as follows: (1), beta-CD (cyclodextrin) is added to a NaOH solution with certain concentration, and the mixture is heated and stirred until beta-CD is completely dissolved; (2), a cross-linking agent is slowly and dropwise added to the solution, the temperature of the solution is maintained, and the mixture is continuously stirred to react for 30-60 min; (3), CaCO3 and an appropriate quantity of cross-linking agents are sequentially added to the solution, the temperature of the solution is maintained, and the mixture is continuously stirred until the solution solidifies; (4), CaCO3 in a solidified product is removed, and vacuum drying is performed after the product is washed with distilled water. The preparation method has the advantages that obtained polymer microspheres have a higher specific surface area, and the state of pores can be controlled by changing the shapes, the sizes and the quantity of CaCO3 particles; the problems that a preparation process adopting an emulsion template method is tedious, a large quantity of raw materials of a reagent are required and the cost is high are solved; the obtained polymer microspheres have good dispersity and have a loose structure, the problem of difficulty in crushing after drying is solved, and meanwhile, the mass transfer rate is effectively increased during application.
Description
Technical field
The present invention relates to porous polymer preparation field, particularly relate to a kind of preparation method of porous cyclodextrin.
Background technology
Beta-cyclodextrin (β-Cyclodextrin, be called for short β-CD) be the cyclodextrin the most extensively utilized at present, β-CD is that outer is hydrophilic and inner chamber is hydrophobic, there is the reactivity similar to cyclodextrin (CD), inclusion compound can be formed with guest molecule generation inclusion complexation effect, some are volatile, labile, easy pollution, the guest molecule inclusion of not easily preserving, thus avoid the generation of the problems referred to above.In poromeric preparation method, template is considered to one of method the most easily and effectively, and the structure of polymerisate and pattern can be regulated easily by the parameter such as kind, size, shape changing template.And emulsion template method is wherein topmost method.At present, the preparation method of cyclodextrin, mainly based on emulsion template method, adopts the emulsifier systems such as vacuum pump oil, whiteruss, tween 80 to prepare cyclodextrin microsphere as emulsion template.But emulsion template method is prepared cyclodextrin microsphere and still be there is the problem that preparation process is comparatively loaded down with trivial details, source chemicals large usage quantity, cost are higher.In addition, the cyclodextrin prepared by letex polymerization can form hard block usually when drying, causes the following process such as pulverizing difficulty, and rate of mass transfer when its closely knit structure reduces application, causes processing efficiency on the low side.
Summary of the invention
The object of this invention is to provide the porous cyclodextrin preparation method that one take calcium carbonate as template and separant (solid dispersion), this preparation method has the advantage that step is simple, cost is low, and the porous cyclodextrin prepared by present method has the feature of short texture, good dispersity, high adsorption capacity.
Technical scheme of the present invention comprises the steps:
(1) appropriate β-CD being added massfraction is in the NaOH solution of 20 ~ 30%, heats and be stirred to β-CD to dissolve completely;
(2) in solution, slowly drip linking agent, dropwise rear continuation stirring reaction 30 ~ 60min;
(3) in solution, CaCO is added
3, again add appropriate linking agent afterwards, continue stirring until solution and solidify;
(4) product solidify to form is dissolved the CaCO removed wherein by salt acid etch
3, then through distilled water flushing to neutral, after vacuum-drying, obtain solid-state porous cyclodextrin,
Described step (2) and step (3) are that the constant basis of homo(io)thermism after maintaining step (1) heating is carried out.
In step (1), the effect of described NaOH solution is to provide the alkaline environment being beneficial to β-CD and dissolving, and preferably, the ratio of the quality addition of described NaOH solution and β-CD is 1.5 ~ 2:1.
The preferred epoxy chloropropane of described linking agent, when linking agent is epoxy chloropropane, addition in step (2) neutralization procedure (3) is 0.4 ~ 0.6 times of β-CD quality addition, and the dropping mode of epoxy chloropropane in step (2) is dripped with the speed of 1mL/6min by constant pressure funnel, make epoxy chloropropane give full play to crosslinked action, contribute to the formation of beta-cyclodextrin oligomer in reaction system.
The described CaCO added in step (3)
3except as template, the effect of separant and pore-creating agent can also be played, after the polyreaction of step (3) terminates, remove the CaCO in polymer microballoon by hydrochloric acid
3namely particle obtains pore space structure.Described CaCO
3addition can determine according to the concrete pore demand of polymkeric substance, in technical solution of the present invention, CaCO
3be 1 ~ 5:1 with the mol ratio of β-CD addition.
In order to ensure reaction and treatment effect, the assisted reaction of each step or treatment condition are preferably as follows: the mixing speed in step (2) and step (3) reaction process is 400 ~ 600r/min; Vacuum-drying temperature in step (4) is 100 DEG C ~ 120 DEG C, and time of drying is 24 ~ 48h.
Technical solution of the present invention adopts calcium carbonate to be that template carrys out alternative traditional emulsion template method, its advantage is: (1) calcium carbonate is in the course of the polymerization process except rapping plate effect, also play the effect of solid dispersion, the porous cyclodextrin microballoon obtained has higher specific surface area, and can regulate and control hole state easily by the shape of change calcium carbonate particles, size and consumption; (2) on processing step, it is simpler compared with emulsion template method that the polymkeric substance preparation in early stage of technical solution of the present invention and later stage calcium carbonate remove process; Effectively prevent simultaneously the reagent such as oil, emulsifying agent raw material dosage cause greatly cost high, recycle loaded down with trivial details problem; (3) the porous cyclodextrin microballoon obtained has good dispersiveness, the difficulty caused following process such as pulverizing after its loose structure avoids drying, effectively improves rate of mass transfer time its application (as immobilized in water depth process, chromatographic separation, medicine with discharge) simultaneously.
Accompanying drawing illustrates:
The ordinary optical microscope of Fig. 1 embodiment of the present invention 1 sample surfaces observes figure.
Fig. 2 embodiment of the present invention 1 sample under different amounts to the adsorption efficiency graphic representation of aniline.
Fig. 3 embodiment of the present invention 1 sample is at the adsorption efficiency comparison diagram of different time sections to aniline.
Embodiment
Below in conjunction with specific embodiment, technical solution of the present invention and effect thereof are described further.
Embodiment 1
(1) 11.35g (0.01mol) β ﹣ CD is got in three neck round-bottomed flasks, adding 17.6mL (22.44g) massfraction is the NaOH solution of 25%, afterwards flask is placed in thermostat water bath and is progressively warming up to 60 DEG C, stirring is aided with, until β ﹣ CD dissolves completely in temperature-rise period;
(2) flask is continued be placed in the temperature of reaction that thermostat water bath keeps 60 DEG C, in solution, slowly 5mL epoxy chloropropane is dripped with the speed of 1mL/6min by constant pressure funnel, it is made to dissolve while dropping, thus give full play to crosslinked action, make in reaction system, to form beta-cyclodextrin oligomer; After dropping terminates, continue stirring reaction 60min with 400 ~ 600r/min rotating speed;
(3) continue maintenance 60 DEG C of temperature of reaction, in solution, add 1g (0.01mol) CaCO
3, again add 5mL epoxy chloropropane afterwards, continue stirring reaction with 400 ~ 600r/min rotating speed and solidify to solution;
(4) product solidify to form is dissolved the CaCO removed wherein by salt acid etch
3, then through distilled water flushing to neutral, after 105 DEG C of vacuum-drying 24h, namely obtain solid-state porous cyclodextrin.
The step that embodiment 2 ~ 4 adopts is substantially the same manner as Example 1, and difference is embodiment 2 ~ 4 CaCO in described step (3)
3addition be respectively 2g (0.02mol), 4g (0.04mol) and 5g (0.05mol).
Performance test
(1) take a morsel the porous cyclodextrin sample obtained by embodiment 1, observes sample surfaces with ordinary optical microscope.Result is as shown in Figure 1: under ordinary optical microscope 100 times (10 times of eyepiece x10 times object lens) magnification, namely can be observed sample surfaces be distributed with the hole that more outward appearance is white point-like, this short texture makes the dispersion treatment in sample later stage more easily carry out, only need by simply grinding, also effectively can improve rate of mass transfer time its application (as immobilized in water depth process, chromatographic separation, medicine with discharge) simultaneously.
(2) it is in the 30mL p-nitrophenyl phenol solution of 12.0608mg/L that the porous cyclodextrin (0.8g) of equivalent obtained by embodiment 1 ~ 4 and contrast (the porous cyclodextrin obtained by conventional emulsion polymerization method) join concentration respectively, after standing adsorption 60min, measure and compare 5 kinds of polymkeric substance to the adsorption efficiency of p-NP.Result is as shown in table 1:
Table 1 embodiment 1 ~ 4 and contrast are compared the adsorption efficiency of p-NP
As can be seen from Table 1, leave standstill 60min in p-nitrophenyl phenol solution after, by embodiment 1 ~ 4 obtain porous cyclodextrin to the adsorption efficiency of p-NP all higher than the porous cyclodextrin obtained by conventional emulsion polymerization method, embody good adsorptive power, and the adsorptive power being obtained polymer samples by technical solution of the present invention increases along with the increase of calcium carbonate template consumption, illustrate that technical solution of the present invention can regulate and control the hole proterties of polymer microballoon by the mode of the consumption changing calcium carbonate particles, and then change its adsorptive power.
(3) the porous cyclodextrin sample obtained by embodiment 1 being joined concentration respectively with different consumptions is in the 30mL aniline solution of 0.88883 μ g/mL, and standing adsorption, after 60 minutes, measures and compares adsorption efficiency.Result is as shown in Figure 2: when the addition of sample is 1.5g, leave standstill after 60 minutes to the adsorption efficiency of aniline close to 0.9, when the addition of sample is 3g, corresponding adsorption efficiency, more than 0.9, shows that the porous cyclodextrin sample obtained by technical solution of the present invention can be issued to the adsorptive power stronger to aniline in the situation of less consumption.
(4) to concentration be 1.009472 μ g/mL 30mL aniline solution in add the porous cyclodextrin sample that 1.2g obtains by embodiment 1, respectively standing adsorption 0,5,10,15,30,45,60,90, after 120min, measure and compare adsorption efficiency.Result as shown in Figure 2.As can be seen from the figure, after 15min, namely sample reaches the adsorption efficiency after 0.7,60min to the adsorption efficiency of aniline and namely reaches about 0.85, shows that sample can reach preferably adsorptive power at short notice.
Claims (6)
1. a porous cyclodextrin preparation method, is characterized in that comprising the following steps:
(1) appropriate β-CD being added massfraction is in the NaOH solution of 20 ~ 30%, heats and be stirred to β-CD to dissolve completely;
(2) in solution, slowly drip linking agent, dropwise rear continuation stirring reaction 30 ~ 60min;
(3) in solution, CaCO is added
3, again add appropriate linking agent afterwards, continue stirring until solution and solidify;
(4) product solidify to form is dissolved the CaCO removed wherein by salt acid etch
3, then through distilled water flushing to neutral, after vacuum-drying, obtain solid-state porous cyclodextrin,
Described step (2) and step (3) are that the constant basis of homo(io)thermism after maintaining step (1) heating is carried out.
2. porous cyclodextrin preparation method according to claim 1, is characterized in that: in described step (3), described CaCO
3be 1 ~ 5:1 with the addition mol ratio of β-CD.
3. porous cyclodextrin preparation method according to claim 1, it is characterized in that: described step (2) and the middle linking agent added of step (3) are epoxy chloropropane, and the addition in step (2) neutralization procedure (3) is 0.4 ~ 0.6 times of described β-CD quality addition.
4. porous cyclodextrin preparation method according to claim 3, is characterized in that: the dropping mode of described epoxy chloropropane in step (2) is: dripped with the speed of 1mL/6min by constant pressure funnel.
5. porous cyclodextrin preparation method according to claim 1, is characterized in that: in described step (1), the ratio of the quality addition of NaOH solution and β-CD is 1.5 ~ 2:1.
6. porous cyclodextrin preparation method according to claim 1, is characterized in that: the mixing speed in described step (2) and step (3) reaction process is 400 ~ 600r/min; Vacuum-drying temperature in step (4) is 100 DEG C ~ 120 DEG C, and time of drying is 24 ~ 48h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589168A (en) * | 2016-12-16 | 2017-04-26 | 中国人民大学 | Beta-cyclodextrin compound, preparation method thereof, and application thereof in water treatment |
| CN106622177A (en) * | 2017-01-12 | 2017-05-10 | 福州大学 | Spherical porous adsorbent based on carbon nanotubes as well as preparation method and application of spherical porous adsorbent |
| CN107159162A (en) * | 2017-06-08 | 2017-09-15 | 中国石油大学(华东) | A kind of polymeric cyclodextrins desulfurizing agent for Light Oil Desulfurization |
| CN110330671A (en) * | 2019-05-10 | 2019-10-15 | 天津科技大学 | A kind of preparation method of cyclodextrin microsphere |
| CN111440029A (en) * | 2020-04-03 | 2020-07-24 | 雷军 | Traditional Chinese medicine residue slow-release fertilizer |
| CN112138636A (en) * | 2020-08-19 | 2020-12-29 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589168A (en) * | 2016-12-16 | 2017-04-26 | 中国人民大学 | Beta-cyclodextrin compound, preparation method thereof, and application thereof in water treatment |
| CN106622177A (en) * | 2017-01-12 | 2017-05-10 | 福州大学 | Spherical porous adsorbent based on carbon nanotubes as well as preparation method and application of spherical porous adsorbent |
| CN106622177B (en) * | 2017-01-12 | 2019-08-09 | 福州大学 | A kind of spherical porous adsorbent and the preparation method and application thereof based on carbon nanotube |
| CN107159162A (en) * | 2017-06-08 | 2017-09-15 | 中国石油大学(华东) | A kind of polymeric cyclodextrins desulfurizing agent for Light Oil Desulfurization |
| CN107159162B (en) * | 2017-06-08 | 2020-04-24 | 中国石油大学(华东) | Polymerization ring dextrin desulfurizer for light oil product desulfurization |
| CN110330671A (en) * | 2019-05-10 | 2019-10-15 | 天津科技大学 | A kind of preparation method of cyclodextrin microsphere |
| CN110330671B (en) * | 2019-05-10 | 2022-01-18 | 天津科技大学 | Preparation method of cyclodextrin microspheres |
| CN111440029A (en) * | 2020-04-03 | 2020-07-24 | 雷军 | Traditional Chinese medicine residue slow-release fertilizer |
| CN112138636A (en) * | 2020-08-19 | 2020-12-29 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
| CN112138636B (en) * | 2020-08-19 | 2023-04-07 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
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