CN109603771A - A kind of preparation method of magnetic chitosan-montmorillonite nanocomposite microspheres - Google Patents
A kind of preparation method of magnetic chitosan-montmorillonite nanocomposite microspheres Download PDFInfo
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Abstract
A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere, belongs to technical field of material chemistry, prepares KOH/LiOHH first2O/ urea mixed solution, with montmorillonite and nanometer Fe3O4The first mixed liquor is obtained after mixing, it is mixed with chitosan, obtains the second mixed liquor；By the second mixed liquor freezing processing, chitosan/montmorillonite/Fe is obtained after defrosting3O4Nanometer mixed solution, after evacuation and centrifugal degassing, epoxychloropropane is added dropwise, it is stirring evenly and then adding into isooctane, is stirring evenly and then adding into Span-80, second is carried out after stirring and is centrifuged, the solution obtained after second is centrifuged is stirred, be then added in ethanol water and be demulsified, be finally washed with deionized to get.The preparation method is easy to operate, process stabilizing, nontoxic and pollution-free, is suitble to large batch of industrialized production, composite nano-microsphere obtained has high adsorption and magnetic and biodegradability.
Description
Technical field
The present invention relates to a kind of chitosan magnetic-montmorillonite microballoons and preparation method thereof, belong to technical field of material chemistry.
Background technique
Microballoon has many characteristics, such as the features such as specific surface area, electric conductivity, magnetism, spherical shape, can be used to design various
The new material of various kinds, has been widely used in water process, the fields such as additive of bio-medical or rubber product.
Natural polymer has abundance and biodegradability, not can cause environmental pollution, natural polymer material
Expect to contain a large amount of amino and hydroxyl in chitosan molecule chain, so as to by the chemical bonds such as hydrogen bond, coordinate bond and from
Organic matter, heavy metal and a variety of anionic species in sub- exchange interaction trapping water, have good adsorptivity, bio-compatible
Property, nontoxicity and biodegradable, it is without secondary pollution the advantages that so that based on days such as cellulose, chitin and chitosans
The microballoon of right macromolecule building is very noticeable in the water treatment fields such as heavy metal and Dye Adsorption.However, most of
Natural polymer microballoon (such as chitosan microball) absorption property is weaker, while being inconvenient to recycle and utilize again.And conventional shell gathers
Sugared microballoon is easily protonated in an acidic solution and dissolves, thus cannot use and carry out heavy metal ion in an acidic solution
Elution.
Summary of the invention
The purpose of the present invention is to provide a kind of chitosan magnetic-montmorillonite-based nano complex microsphere, which has high inhale
Attached property, is convenient for recycling and reusing and biodegradability at acid resistance.
Another object of the present invention is to provide above-mentioned chitosan magnetic-montmorillonite-based nano complex microsphere preparation method,
This method is easy to operate, process stabilizing, can very easily complete chitosan/montmorillonite/chitosan/Fe3O4Composite nano-microsphere
Produce.
Technical solution
A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere, includes the following steps:
(1) KOH/LiOHH is prepared2O/ urea mixed solution, by itself and montmorillonite and nanometer Fe3O4It is uniformly mixed, obtains
To the first mixed liquor；
(2) the first mixed liquor is mixed with chitosan, obtains the second mixed liquor；
(3) the second mixed liquor is subjected to freezing processing, then thaws, obtains chitosan/montmorillonite/Fe3O4Nanometer mixing is molten
Liquid；
(4) by chitosan/montmorillonite/Fe3O4After nanometer mixed solution evacuation and centrifugal degassing, dripped into the solution after evacuation and centrifugal degassing
Add epoxychloropropane, add isooctane after mixing evenly, after mixing evenly, Span-80 is added, carried out after stirring second from
The heart, will second be centrifuged after obtained solution be stirred, be then added in ethanol water and be demulsified, then spend from
Sub- water washing is to get chitosan magnetic-montmorillonite-based nano complex microsphere.
Further, in step (1), the KOH/LiOHH2In O/ urea mixed solution, the mass concentration of KOH is 5~
10%, LiOHH2The mass concentration of O is 5~10%, and the mass concentration of urea is 5~10%.When preparing the mixed solution,
It only needs for three kinds of substances to be added sequentially in water, be sufficiently stirred.Specifically, the proportion influence chitosan of mixed solution exists
Solubility in solution, the change of ratio may cause chitosan and cannot be completely dissolved.
Further, in step (1), the uniformly mixed mode are as follows: first 1~5h of mechanical stirring, it is then sonicated 10~
30min.It can not make raw material mixing in the independent mechanical stirring short time sufficiently, first mechanical stirring ultrasonic better effect again.
Further, in step (2), mass concentration of the chitosan in the second mixed liquor is 2~5%.The concentration can make
Montmorillonite is better dispersed on chitosan, and the chitosan/montmorillonite/chitosan/Fe3O4 composite nano-microsphere made is more
It is regular.
Further, in step (3), the condition of the freezing processing are as follows: temperature≤- 30 DEG C, cooling time are 1~8h.Institute
The mode for stating defrosting is natural thaw at room temperature.
Further, in step (4), the condition of the evacuation and centrifugal degassing are as follows: temperature be -10~0 DEG C, revolving speed be 6000~
8000r/min, 8~15min of centrifugation time.Low-temperature centrifugation can guarantee chitosan/montmorillonite-based nano mixed solution mobility,
Facilitate the gas in removing chitosan/montmorillonite-based nano mixed solution, the composite nano-microsphere quality made is more evenly.
Further, in step (4), the dosage of epoxychloropropane is that 0.5-3mL is added in every 100g mixed liquor.
Further, in step (4), the dosage of Span-80 is the 0.5-2% of isooctane volume fraction.
Further, in step (4), in the ethanol water, the volume ratio of ethyl alcohol and water is 7:3.
Beneficial effects of the present invention: the present invention provides a kind of chitosan magnetic-montmorillonite-based nano complex microspheres, have
High adsorption, acid resistance and biodegradability are convenient for recycling and reusing, and especially suitable for water treatment field, and preparing should
The method of composite nano-microsphere is easy to operate, process stabilizing, nontoxic and pollution-free, not high to equipment requirement.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of CF-3 type microballoon made from embodiment 1；
Fig. 2 is the stereoscan photograph of CF-4 type microballoon made from embodiment 2；
Fig. 3 is that CF-3 type and CF-4 type microballoon impregnate the microscope photo after hydrochloric acid solution；
Fig. 4 is responsiveness photo of the CF-3 type microballoon for magnet.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Embodiment 1
A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere, includes the following steps:
(1) 7g potassium hydroxide, 7g lithium hydroxide (LiOHH are weighed with the beaker of 250mL2O), 75g is added in 8g urea
Water is placed in ultrasonic machine and carries out ultrasonic dissolution, obtains KOH/LiOHH2O/ urea mixed solution, by its with 0.3g montmorillonite with
And 0.45g nanometer Fe3O4It is uniformly mixed, obtains the first mixed liquor；
(2) the first mixed liquor is mixed with 3g chitosan, obtains the second mixed liquor；
(3) the second mixed liquor is freezed into 2h under conditions of -30 DEG C, then thawed, obtain chitosan/montmorillonite/Fe3O4
Nanometer mixed solution；
(4) by chitosan/montmorillonite/Fe3O4(environment is -8 DEG C to nanometer mixed solution evacuation and centrifugal degassing, revolving speed 7000rpm/
Min) after 10min, solution 20g after taking evacuation and centrifugal degassing is added dropwise 0.4mL epoxychloropropane, magnetite is put into, on magnetic stirring apparatus
30min is stirred, 100mL isooctane is added when stirring 15min, is transferred in three-necked flask, under conditions of 400rpm/min
It is stirred, 1mL Span-80 is added, carry out second centrifugation (identical as first time parameter of noncentricity) after stirring 30min, by the
The solution stirring 2h obtained after secondary centrifuging is then added in 200mL ethanol water (volume ratio of ethyl alcohol and water is 7:3)
It is demulsified, is then washed with deionized to get chitosan magnetic-montmorillonite-based nano complex microsphere, be denoted as CF-3 type microballoon.
The stereoscan photograph of CF-3 type microballoon is shown in Fig. 1, it can be seen that shows the illiteracy of the sheet of white in microsphere surface
De- soil, illustrates that montmorillonite is successfully introduced in microballoon.The particle diameter distribution of CF-3 type microballoon is shown in Table 1:
1 CF-3 particle diameter distribution of table
Embodiment 2
A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere, includes the following steps:
(1) 7g potassium hydroxide, 7g lithium hydroxide (LiOHH are weighed with the beaker of 250ml2O), 74g is added in 8g urea
Water is placed in ultrasonic machine and carries out ultrasonic dissolution, obtains KOH/LiOHH2O/ urea mixed solution, by its with 0.3g montmorillonite with
And 0.45g nanometer Fe3O4It is uniformly mixed, obtains the first mixed liquor；
(2) the first mixed liquor is mixed with 4g chitosan, obtains the second mixed liquor；
(3) the second mixed liquor is freezed into 2h under conditions of -30 DEG C, then thawed, obtain chitosan/montmorillonite/Fe3O4
Nanometer mixed solution；
(4) by chitosan/montmorillonite/Fe3O4(environment is -8 DEG C to nanometer mixed solution evacuation and centrifugal degassing, revolving speed 7000rpm/
Min) after 10min, solution 20g after taking evacuation and centrifugal degassing is added dropwise 0.4mL epoxychloropropane, magnetite is put into, on magnetic stirring apparatus
30min is stirred, 100mL isooctane is added when stirring 15min, is transferred in three-necked flask, under conditions of 400rpm/min
It is stirred, 1mL Span-80 is added, carry out second centrifugation (identical as first time parameter of noncentricity) after stirring 30min, by the
The solution stirring 2h obtained after secondary centrifuging is then added in 200mL ethanol water (volume ratio of ethyl alcohol and water is 7:3)
It is demulsified, is then washed with deionized to get chitosan magnetic-montmorillonite-based nano complex microsphere, be denoted as CF-4 type microballoon.
The stereoscan photograph of CF-4 type microballoon is shown in Fig. 2, it can be seen that small of many protrusions is shown on figure d
Grain, the composition of particle is Fe3O4.The particle diameter distribution of CF-4 type microballoon is shown in Table 2:
2 CF-4 particle diameter distribution of table
Embodiment 3
A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere, includes the following steps:
(1) 7g potassium hydroxide, 7g lithium hydroxide (LiOHH are weighed with the beaker of 250ml2O), 73g is added in 8g urea
Water is placed in ultrasonic machine and carries out ultrasonic dissolution, obtains KOH/LiOHH2O/ urea mixed solution, by its with 0.3g montmorillonite with
And 0.45g nanometer Fe3O4It is uniformly mixed, obtains the first mixed liquor；
(2) the first mixed liquor is mixed with 5g chitosan, obtains the second mixed liquor；
(3) the second mixed liquor is freezed into 2h under conditions of -30 DEG C, then thawed, obtain chitosan/montmorillonite/Fe3O4
Nanometer mixed solution；
(4) by chitosan/montmorillonite/Fe3O4(environment is -8 DEG C to nanometer mixed solution evacuation and centrifugal degassing, revolving speed 7000rpm/
Min) after 10min, solution 20g after taking evacuation and centrifugal degassing is added dropwise 0.1mL epoxychloropropane, magnetite is put into, on magnetic stirring apparatus
30min is stirred, 100mL isooctane is added when stirring 15min, is transferred in three-necked flask, under conditions of 400rpm/min
It is stirred, 0.5mL Span-80 is added, carry out second of centrifugation (identical as first time parameter of noncentricity) after stirring 30min, it will
The solution stirring 2h obtained after second of centrifugation is then added to 200mL ethanol water (volume ratio of ethyl alcohol and water is 7:3)
In be demulsified, be then washed with deionized to get chitosan magnetic-montmorillonite-based nano complex microsphere, it is micro- to be denoted as CF-5 type
Ball.
3 CF-5 particle diameter distribution of table
Embodiment 4
A kind of preparation method of chitosan magnetic-montmorillonite-based nano complex microsphere, includes the following steps:
(1) 7g potassium hydroxide, 7g lithium hydroxide (LiOHH are weighed with the beaker of 250ml2O), 76g is added in 8g urea
Water is placed in ultrasonic machine and carries out ultrasonic dissolution, obtains KOH/LiOHH2O/ urea mixed solution, by its with 0.3g montmorillonite with
And 0.45g nanometer Fe3O4It is uniformly mixed, obtains the first mixed liquor；
(2) the first mixed liquor is mixed with 2g chitosan, obtains the second mixed liquor；
(3) the second mixed liquor is freezed into 2h under conditions of -30 DEG C, then thawed, obtain chitosan/montmorillonite/Fe3O4
Nanometer mixed solution；
(4) by chitosan/montmorillonite/Fe3O4(environment is -8 DEG C to nanometer mixed solution evacuation and centrifugal degassing, revolving speed 7000rpm/
Min) after 10min, solution 20g after taking evacuation and centrifugal degassing is added dropwise 0.6mL epoxychloropropane, magnetite is put into, on magnetic stirring apparatus
30min is stirred, 100mL isooctane is added when stirring 15min, is transferred in three-necked flask, under conditions of 400rpm/min
It is stirred, 2mL Span-80 is added, carry out second centrifugation (identical as first time parameter of noncentricity) after stirring 30min, by the
The solution stirring 2h obtained after secondary centrifuging is then added in 200mL ethanol water (volume ratio of ethyl alcohol and water is 7:3)
It is demulsified, is then washed with deionized to get chitosan magnetic-montmorillonite-based nano complex microsphere, be denoted as CF-2 type microballoon.
4 CF-2 particle diameter distribution of table
Performance test
CF-3 and CF-4 type microballoon made from the method for embodiment 1-2 is carried out to the test of adsorptivity, acid resistance and magnetism,
The specific test method is as follows:
1. copper absorption is tested
3g copper sulphate is weighed with pan paper, is then transferred into the beaker of 250ml, 100g deionized water is added, is prepared into
The solution that copper-bath concentration is 3% remains spare.The copper ion solution for taking out 15ml is transferred to conduct in the beaker of 50ml
Original solution, with diaphragm seal, the copper ion solution for further taking out 15ml is transferred in beaker, is stood, sealing.Taking-up gathers micro-
Ball, CF-3 the and CF-4 microballoon of 150 mesh, is individually positioned on glass dish, puts and dries for 24 hours in the environment of 70 DEG C in an oven, so
Dry weight is weighed on assay balance afterwards, is then transferred in copper ion solution and carries out absorption 24 hours, then isolate absorption with funnel
Microballoon afterwards, then the quality for further taking out be placed on after weighing absorption on assay balance for 24 hours is dried under conditions of 70 DEG C in an oven, it is real
It tests and the results are shown in Table 5:
5 CF-3 and CF-4 type microballoon of table be immersed in copper ion solution for 24 hours after quality versus
As can be seen that the copper absorption ability of CF-4 type microballoon is relatively high.
2. Dye Adsorption is tested
0.3g basic fuchsin reagent is weighed, is then transferred into the beaker of 250ml, 200g deionized water is added, is used
Stirring rod, ultrasonic oscillation instrument are dissolved, and the dye solution of saturated concentration is prepared into.Take out the microballoon gathered, 150 purposes
CF-3 and CF-4 microballoon, is individually positioned on glass dish, puts and dries for 24 hours in the environment of 70 DEG C in an oven, is then transferred to dyestuff
Absorption 24 hours is carried out in solution, then the microballoon after isolating absorption with funnel, then dry for 24 hours under conditions of 70 DEG C in an oven.
The experimental results showed that the color of microballoon is rendered as brown before absorption, it is mainly to be received because joined magnetism
Rice corpuscles Fe3O4The reason of, impregnated in dye solution for 24 hours and after drying, kermesinus is presented in the color of microballoon, illustrate CF-3 and
CF-4 microballoon has the ability of certain absorption to basic fuchsin.
3. resistance to dilute hydrochloric acid test
97.3ml deionized water is first added, then using syringe to draw 2.7ml concentration is 36% concentrated hydrochloric acid in the burning of 250ml
In cup, being stirred with glass bar, be configured to 1% solution, the solution for taking out 50ml is transferred in the beaker of 250ml, then plus
Enter deionized water, is configured to 0.5% solution.The microballoon of 200 mesh of CF-3 type and CF-4 type is taken to be put into 1% respectively
Hydrochloric acid solution and 0.5% hydrochloric acid solution in, impregnate for 24 hours, then observe the state of microballoon under the microscope, and test CF-3 type
Partial size after being impregnated for 24 hours in hydrochloric acid solution with CF-4 type microballoon.
CF-3 type and CF-4 type microballoon impregnate the microscope photo after hydrochloric acid solution and see Fig. 3, it can be seen that CF-3 type and
CF-4 type microballoon remains the shape of ball, it may be said that bright microballoon has the performance of weak acid resistant.
Partial size after CF-3 type and CF-4 type microballoon impregnate for 24 hours in hydrochloric acid solution is shown in Table 6:
6 CF-3 type of table and CF-4 type microballoon impregnated for 24 hours in hydrochloric acid solution after partial size
After CF-3 type and CF-4 type microballoon impregnate for 24 hours in dilute hydrochloric acid hydrochloric acid as can be seen from Table 4, the volume of microballoon is obvious
Increase, CF-3 partial size averagely increases 50%, CF-4 partial size and averagely increases 65%.
4. Magnetic Test
The excellent magnetic separation for microballoon and recycling are significant, we are using simply by one block of magnet herein
Complex microsphere CF-3 is tested to the responsiveness of magnet, microballoon is dispersed in first the distilled water solution being contained in plastic tube
In, it allows microballoon to be deposited to distilled water bottom under the effect of gravity, then takes one block of magnet close to plastic tube, observe microballoon in magnet
Migration situation under effect.
Magnetic Test result: Fig. 4 is responsiveness photo of the CF-3 type microballoon for magnet, and before a- leans near magnet, b- is close
After magnet, it can be seen that under the action of external magnetic field, CF-3 type microballoon leans on rapidly near magnet in 5 seconds.It can be seen that preparation
Microballoon have good magnetic responsiveness.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (8)
1. a kind of chitosan magnetic-montmorillonite-based nano complex microsphere preparation method, which comprises the steps of:
(1) KOH/LiOHH is prepared2O/ urea mixed solution, by itself and montmorillonite and nanometer Fe3O4It is uniformly mixed, obtains the
One mixed liquor；
(2) the first mixed liquor is mixed with chitosan, obtains the second mixed liquor；
(3) the second mixed liquor is subjected to freezing processing, then thaws, obtains chitosan/montmorillonite/Fe3O4Nanometer mixed solution；
(4) by chitosan/montmorillonite/Fe3O4After nanometer mixed solution evacuation and centrifugal degassing, ring is added dropwise into the solution after evacuation and centrifugal degassing
Oxygen chloropropane adds isooctane after mixing evenly, after mixing evenly, Span-80 is added, and second is carried out after stirring and is centrifuged,
The solution obtained after second is centrifuged is stirred, and is then added in ethanol water and is demulsified, then uses deionization
Water washing is to get chitosan magnetic-montmorillonite-based nano complex microsphere.
2. chitosan magnetic as described in claim 1-montmorillonite-based nano complex microsphere preparation method, which is characterized in that step
(1) in, the KOH/LiOHH2In O/ urea mixed solution, the mass concentration of KOH is 5~10%, LiOHH2The quality of O
Concentration is 5~10%, and the mass concentration of urea is 5~10%.
3. chitosan magnetic as described in claim 1-montmorillonite-based nano complex microsphere preparation method, which is characterized in that step
(2) in, mass concentration of the chitosan in the second mixed liquor is 2~5%.
4. chitosan magnetic as described in claim 1-montmorillonite-based nano complex microsphere preparation method, which is characterized in that step
(3) in, the condition of the freezing processing are as follows: temperature≤- 30 DEG C, cooling time are 1~8h.
5. chitosan magnetic as described in claim 1-montmorillonite-based nano complex microsphere preparation method, which is characterized in that step
(4) in, the condition of the evacuation and centrifugal degassing are as follows: temperature be -10~0 DEG C, revolving speed be 6000~8000r/min, centrifugation time 8~
15min。
6. chitosan magnetic as described in claim 1-montmorillonite-based nano complex microsphere preparation method, which is characterized in that step
(4) in, the dosage of epoxychloropropane is that 0.5-3mL is added in every 100g mixed liquor.
7. chitosan magnetic as described in claim 1-montmorillonite-based nano complex microsphere preparation method, which is characterized in that into one
It walks, in step (4), the dosage of Span-80 is the 0.5-2% of isooctane volume fraction.
8. chitosan magnetic-montmorillonite-based nano complex microsphere preparation method, feature as described in any one of claim 1 to 7
It is, in step (4), in the ethanol water, the volume ratio of ethyl alcohol and water is 7:3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110064379A (en) * | 2019-05-27 | 2019-07-30 | 广西壮族自治区农业科学院 | The preparation method of the chitosan magnetic composite material of methyl orange in a kind of absorption effluent |
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| CN114479165B (en) * | 2022-02-28 | 2023-10-24 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
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| CN114984916B (en) * | 2022-04-26 | 2024-03-08 | 贵州黔大生态环境与健康研究院有限公司 | Chitosan nano microsphere, preparation method and application thereof |
| CN115254044A (en) * | 2022-04-29 | 2022-11-01 | 湖州师范学院 | Preparation method of magnetic bentonite-gelatin composite microspheres for removing Cu ions in water body sediment |
| CN115254044B (en) * | 2022-04-29 | 2024-02-06 | 湖州师范学院 | Preparation method of magnetic bentonite gelatin composite microsphere for removing Cu ions in water bottom mud |
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