CN103007892A - Preparation method for magnetic polymer composite microsphere - Google Patents
Preparation method for magnetic polymer composite microsphere Download PDFInfo
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- CN103007892A CN103007892A CN2012105203268A CN201210520326A CN103007892A CN 103007892 A CN103007892 A CN 103007892A CN 2012105203268 A CN2012105203268 A CN 2012105203268A CN 201210520326 A CN201210520326 A CN 201210520326A CN 103007892 A CN103007892 A CN 103007892A
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Abstract
The invention provides a preparation method for a magnetic polymer composite microsphere, which relates to a preparation method for an inorganic-organic composite material and a functional polymer composite material. The method comprises the following steps: 1) preparation of a nanometer Fe3O4 particle: a step of adding an alkaline solution into a compound solution containing Fe<3+> and Fe<2+> drop by drop under the protection of N2 and then carrying out solid-liquid separation, washing and vacuum drying; 2) preparation of a magnetic calcium alginate gel sphere: a step of uniformly mixing the nanometer Fe3O4 particle with calcium alginate gel and removing Cl<-> on the surface of the gel sphere through washing with water; and 3) preparation of the magnetic polymer composite microsphere: a step of adding the magnetic calcium alginate gel sphere into an acid solution of chitosan, immersing the gel sphere in glutaraldehyde and carrying out magnetic separation and vacuum drying so as to obtain the magnetic polymer composite microsphere. The method provided by the invention has the advantages of easy availability of raw materials, simple operation, high efficiency and the like; and the prepared microsphere has a uniform size, high thermal stability and mechanical stability and a strong adsorptive property, can be recovered and reused and is applicable to fields like wastewater treatment.
Description
Technical field
The present invention relates to the preparation method of a kind of organic-inorganic composite material and functional polymer composites, particularly relate to a kind of preparation method of magnetic composite microsphere.
Background technology
Chitosan molecule is to be only second to cellulosic second largest natural polysaccharide, owing to having the functional groups such as a large amount of hydroxyls, amino in the chitosan molecule, therefore can be used as the novel material for water treatment such as adsorbent, flocculant.Studies show that, shitosan class adsorbent has preferably removal effect to heavy metal ion in the water.But the mechanical performance of shitosan is relatively poor, usually will carry out chemical modification and physical modification to it.Glutaraldehyde is often used as crosslinking agent, prevents that shitosan from dissolving in acid solution.Alginate is a kind of natural polymer, is anionic polyelectrolyte, and elementary cell is mannuronic acid and guluronic acid.On the alginate-COOH can with shitosan on-NH
2Carry out bonding by electrostatic interaction.Studies show that, the adsorbent behind the bonding has the good characteristic of two kinds of polymer concurrently, has preferably adsorption of metal ions performance.Although such adsorbent can effectively be removed heavy metal ion in the water, adsorb the adsorbent Separation of Solid and Liquid difficulty after saturated, operation is wasted time and energy, and therefore is necessary to develop the effectively compound adsorbent of Separation of Solid and Liquid.Magnetic adsorbent can add fast separation of realization under the magnetic field condition, can effectively solve the problem of adsorbent Separation of Solid and Liquid difficulty.Magnetic macromolecular microsphere has numerous characteristics and the magnetic response performance of polymer microsphere, absorption affinity is strong, its surface can be in conjunction with various functional moleculars, such as enzyme, antibody, cell, DNA or RNA etc., thereby be widely used in fields such as wastewater treatment, bio-separation, magnetic target administration, immobilised enzymes, immunoassay and mensuration and biochemistry are synthetic.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of magnetic composite microsphere, the magnetic Ah-ACMS complex microsphere of preparation is used for Cu
2+Adsorption experiment, the initial reaction condition is: Cu
2+Initial concentration 50 mg/L, Cu
2+Clearance can reach 97%.The complex microsphere of preparation has that magnetic response performance, absorption affinity are strong, effective Separation of Solid and Liquid.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of magnetic composite microsphere comprises being prepared as follows step:
(1) will contain Fe
3+, Fe
2+Compound add there-necked flask, logical N
2Protection, heating water bath to 50 ℃ under the rapid stirring condition, at the uniform velocity drips alkaline aqueous solution in there-necked flask, regulator solution pH value is greater than 9, rapid stirring 0.5-1 h is warming up to 75 ℃, insulation slaking 0.5-1 h, Separation of Solid and Liquid, at the 25 ℃ of lower ultrasonic processing of ethanol/water solution 1-2 h with 1:1, washing is in 80-100 ℃ of vacuum drying;
(2) at room temperature, with Fe
3O
4Nano particle slowly drops to CaCl with magnetic gel with after sodium alginate gel is evenly mixed with syringe
2Balling-up in the solution behind the ageing 12-36 h, is washed the Cl on gel ball surface off with deionized water
-
(3) at room temperature, the magnetic high-molecular gel ball is joined in the acid solution of shitosan, after slowly stirring 12-36 h, gel beads is immersed in the glutaraldehyde, slowly stirs 12-36 h, Magnetic Isolation, with deionized water and absolute ethanol washing, 60-80 ℃ of vacuum drying, obtain magnetic composite microsphere, grind into powder is for subsequent use.
The preparation method of described a kind of magnetic composite microsphere, its described Fe
3+Salt is FeCl
3, Fe (NO
3)
3, Fe
2(SO
4)
3, NH
4Fe (SO
4)
2In one or more, described Fe
2+Salt is FeCl
2, Fe (NO
3)
2, FeSO
4, (NH
4)
2Fe (SO
4)
2In one or more.
The preparation method of described a kind of magnetic composite microsphere, its described Fe
3+Salt and Fe
2+The mol ratio of salt is 5:(1 ~ 10).
The preparation method of described a kind of magnetic composite microsphere, its described alkaline aqueous solution is NH
4A kind of in OH solution, LiOH solution, NaOH solution, the KOH solution.
The preparation method of described a kind of magnetic composite microsphere, its described sodium alginate gel concentration is 1% ~ 10%, described CaCl
2Solution concentration is 1% ~ 10%.
The preparation method of described a kind of magnetic composite microsphere, its described chitosan solution mass percent concentration is 1% ~ 10%, described shitosan and weight of iron are than 100:(1 ~ 1000).
The preparation method of described a kind of magnetic composite microsphere, its described acid solution is one or more in formic acid, acetic acid, citric acid, watery hydrochloric acid, dilute sulfuric acid, the rare nitric acid, the mass percent concentration of acid is 1% ~ 15%.
The preparation method of described a kind of magnetic composite microsphere, its described stir speed (S.S.) is 500 ~ 1000r/min, stir speed (S.S.) is 50 ~ 100r/min.
Advantage of the present invention and effect are:
1. preparation method of the present invention is simple, and whole process can be finished under temperate condition, and common laboratory, medium-sized and small enterprises can prepare.
2. raw material of the present invention is cheap and easy to get, and environmental condition takes up room little without specific (special) requirements to external world, and cost of investment is low, easily transforms and goes into operation.
3. magnetic composite microsphere long service life of the present invention is easy to Separation of Solid and Liquid, and does not have secondary pollution problems.
Description of drawings
Fig. 1 is the SEM figure of the magnetic Ah-ACMS complex microsphere of embodiment 1 preparation.
Fig. 2 is the SEM figure of the magnetic Ah-ACMS complex microsphere of embodiment 2 preparations.
Annotate: Fig. 1-Fig. 2 of the present invention is the analysis schematic picture of product state, the unintelligible understanding that does not affect technical solution of the present invention of figure Chinese word or image.
The specific embodiment
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1:
At room temperature, in 250 mL there-necked flasks of magnetic stirring apparatus, dropping funel are housed, add 2.7 g FeCl
36H
2O and 2.8 g FeSO
47H
2O(mol ratio 1:1) is dissolved in the 50mL water logical N
2Protection, heating water bath under the condition of vigorous stirring, at the uniform velocity drips the NaOH solution 50mL of 1.5mol/L to uniform temperature (about 50 ℃) in there-necked flask, regulates the pH value greater than 9.Dropwise, rapid stirring 30min is warming up to 75 ℃, insulation slaking 30min, and Separation of Solid and Liquid, at the 25 ℃ of lower ultrasonic processing of ethanol/water solution 1h with 1:1, washing is in 100 ℃ of vacuum drying; Fe with preparation
3O
4Join in 2% sodium alginate gel evenly mix after, magnetic gel is slowly dropped to 2% CaCl with syringe
2Behind slaking 24 h, wash the Cl on gel ball surface off with deionized water in the solution (100 mL)
-The magnetic gel ball is joined in the chitosan-acetic acid solution of 100 mL 2%, after slowly stirring 24 h, magnetic ball is immersed in 24 h in the glutaraldehyde solution of 0.05 mol/L, Magnetic Isolation is respectively washed 3 ~ 4 times with deionized water and absolute ethyl alcohol, at 70 ℃ of vacuum drying 12 h, obtain magnetic Ah-ACMS complex microsphere, grind into powder is for subsequent use.
The magnetic Ah-ACMS complex microsphere of preparation is used for Cu
2+Adsorption experiment, the initial reaction condition is: Cu
2+Initial concentration 50 mg/L, complex microsphere consumption 2.0 g/L, solution original ph 5.0, adsorption time 5 h, mixing speed 150 r/min, Cu
2+Clearance can reach 95%.
Embodiment 2:
At room temperature, in 250 mL there-necked flasks of magnetic stirring apparatus, dropping funel are housed, add 2.7 g FeCl
36H
2O and 5.6 g FeSO
47H
2O(mol ratio 1:2) is dissolved in the 50mL water logical N
2Protection, heating water bath under the condition of vigorous stirring, at the uniform velocity drips the NaOH solution 50mL of 1.5mol/L to uniform temperature (about 50 ℃) in there-necked flask, regulates the pH value greater than 9.Dropwise, rapid stirring 30min is warming up to 75 ℃, insulation slaking 30min, and Separation of Solid and Liquid, at the 25 ℃ of lower ultrasonic processing of ethanol/water solution 1h with 1:1, washing is in 100 ℃ of vacuum drying; Fe with preparation
3O
4Join in 4% sodium alginate gel evenly mix after, magnetic gel is slowly dropped to 4% CaCl with syringe
2Behind slaking 24 h, wash the Cl on gel ball surface off with deionized water in the solution (100 mL)
-The magnetic gel ball is joined in the chitosan-acetic acid solution of 100 mL 4%, after slowly stirring 24 h, magnetic ball is immersed in 36 h in the glutaraldehyde solution of 0.05 mol/L, Magnetic Isolation is respectively washed 3 ~ 4 times with deionized water and absolute ethyl alcohol, at 70 ℃ of vacuum drying 12 h, obtain magnetic Ah-ACMS complex microsphere, grind into powder is for subsequent use.
The magnetic Ah-ACMS complex microsphere of preparation is used for Cu
2+Adsorption experiment, the initial reaction condition is: Cu
2+Initial concentration 50 mg/L, complex microsphere consumption 2.0 g/L, solution original ph 5.0, adsorption time 5 h, mixing speed 150 r/min, Cu
2+Clearance can reach 97%.
Claims (8)
1. the preparation method of a magnetic composite microsphere is characterized in that, comprises being prepared as follows step:
(1) will contain Fe
3+, Fe
2+Compound add there-necked flask, logical N
2Protection, heating water bath to 50 ℃ under the rapid stirring condition, at the uniform velocity drips alkaline aqueous solution in there-necked flask, regulator solution pH value is greater than 9, rapid stirring 0.5-1 h is warming up to 75 ℃, insulation slaking 0.5-1 h, Separation of Solid and Liquid, at the 25 ℃ of lower ultrasonic processing of ethanol/water solution 1-2 h with 1:1, washing is in 80-100 ℃ of vacuum drying;
(2) at room temperature, with Fe
3O
4Nano particle slowly drops to CaCl with magnetic gel with after sodium alginate gel is evenly mixed with syringe
2Balling-up in the solution behind the ageing 12-36 h, is washed the Cl on gel ball surface off with deionized water
-
(3) at room temperature, the magnetic high-molecular gel ball is joined in the acid solution of shitosan, after slowly stirring 12-36 h, gel beads is immersed in the glutaraldehyde, slowly stirs 12-36 h, Magnetic Isolation, with deionized water and absolute ethanol washing, 60-80 ℃ of vacuum drying, obtain magnetic composite microsphere, grind into powder is for subsequent use.
2. the preparation method of a kind of magnetic composite microsphere according to claim 1 is characterized in that, described Fe
3+Salt is FeCl
3, Fe (NO
3)
3, Fe
2(SO
4)
3, NH
4Fe (SO
4)
2In one or more, described Fe
2+Salt is FeCl
2, Fe (NO
3)
2, FeSO
4, (NH
4)
2Fe (SO
4)
2In one or more.
3. the preparation method of a kind of magnetic composite microsphere according to claim 1 is characterized in that, described Fe
3+Salt and Fe
2+The mol ratio of salt is 5:(1 ~ 10).
4. the preparation method of a kind of magnetic composite microsphere according to claim 1 is characterized in that, described alkaline aqueous solution is NH
4A kind of in OH solution, LiOH solution, NaOH solution, the KOH solution.
5. the preparation method of a kind of magnetic composite microsphere according to claim 1 is characterized in that, described sodium alginate gel concentration is 1% ~ 10%, described CaCl
2Solution concentration is 1% ~ 10%.
6. the preparation method of a kind of magnetic composite microsphere according to claim 1 is characterized in that, described chitosan solution mass percent concentration is 1% ~ 10%, and described shitosan and weight of iron are than 100:(1 ~ 1000).
7. the preparation method of a kind of magnetic composite microsphere according to claim 1, it is characterized in that, described acid solution is one or more in formic acid, acetic acid, citric acid, watery hydrochloric acid, dilute sulfuric acid, the rare nitric acid, and the mass percent concentration of acid is 1% ~ 15%.
8. the preparation method of a kind of magnetic composite microsphere according to claim 1 is characterized in that, described stir speed (S.S.) is 500 ~ 1000r/min, and stir speed (S.S.) is 50 ~ 100r/min.
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|---|---|---|---|
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|---|---|---|---|
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Family
ID=47957324
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Cited By (17)
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|---|---|---|---|---|
| CN103495209A (en) * | 2013-09-26 | 2014-01-08 | 福州大学 | Autofluorescence bone repairing magnetic sustained-release microspheres |
| CN103709422A (en) * | 2013-12-20 | 2014-04-09 | 华南理工大学 | Preparation method of magnetic cellulose nanocrystal |
| CN103801267A (en) * | 2014-02-11 | 2014-05-21 | 江苏大学 | Preparation method for novel magnetic chitosan composite microsphere antibiotic adsorbent |
| CN106107242A (en) * | 2016-07-29 | 2016-11-16 | 舟山市瑞丰生物技术有限公司 | A kind of nonreactive aquatic immune reinforcing agent |
| CN106890678A (en) * | 2017-03-14 | 2017-06-27 | 泰山医学院 | A kind of TiO2Magnetic bead and its application |
| CN106984290A (en) * | 2017-06-02 | 2017-07-28 | 河南工程学院 | The preparation method of the chitosan of adsorbing heavy metal ions/sodium alginate magnetic composite microsphere |
| CN107583616A (en) * | 2017-09-11 | 2018-01-16 | 浙江海洋大学 | A kind of method of arsenic in absorption antarctic krill oil |
| CN108176370A (en) * | 2017-12-22 | 2018-06-19 | 苏州纳贝通环境科技有限公司 | A kind of preparation method of magnetic gel heavy metal absorbent |
| CN105148871B (en) * | 2015-07-21 | 2018-11-02 | 中国农业科学院饲料研究所 | A kind of environmental-friendly absorption zearalenone material and its application |
| CN108823187A (en) * | 2018-05-08 | 2018-11-16 | 南阳师范学院 | A kind of preparation method of cellulase and saccharomycete co-immobilization magnetic microsphere |
| CN109174027A (en) * | 2018-09-19 | 2019-01-11 | 重庆大学 | The preparation method of the fixed aluminium pillared bentonite adsorbent of sodium alginate and its method for adsorbing phosphate radical |
| CN109438732A (en) * | 2018-11-12 | 2019-03-08 | 西安交通大学 | A kind of preparation method of polyvinyl alcohol/chitosan gel rubber pearl |
| CN111036178A (en) * | 2019-12-31 | 2020-04-21 | 深圳容金科技有限公司 | Magnetic microsphere and preparation method thereof |
| CN112844328A (en) * | 2020-12-24 | 2021-05-28 | 武汉理工大学 | Sodium alginate/chitosan quaternary ammonium salt magnetic adsorption gel ball and preparation method and application thereof |
| CN113181199A (en) * | 2021-04-13 | 2021-07-30 | 西安交通大学 | PH-responsive intelligent porous magnetic nano drug delivery system for combined administration of bicalutamide and adriamycin and preparation method thereof |
| CN113443935A (en) * | 2021-07-02 | 2021-09-28 | 浙江工业大学 | Preparation method and application of solidified microspheric fertilizer for soil remediation |
| CN115254046A (en) * | 2022-09-02 | 2022-11-01 | 重庆市生态环境科学研究院 | Functionalized magnetic gel bead with surface modified with metal ions, and preparation method and application thereof |
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| CN103495209A (en) * | 2013-09-26 | 2014-01-08 | 福州大学 | Autofluorescence bone repairing magnetic sustained-release microspheres |
| CN103495209B (en) * | 2013-09-26 | 2015-03-04 | 福州大学 | Autofluorescence bone repairing magnetic sustained-release microspheres |
| CN103709422A (en) * | 2013-12-20 | 2014-04-09 | 华南理工大学 | Preparation method of magnetic cellulose nanocrystal |
| CN103801267A (en) * | 2014-02-11 | 2014-05-21 | 江苏大学 | Preparation method for novel magnetic chitosan composite microsphere antibiotic adsorbent |
| CN105148871B (en) * | 2015-07-21 | 2018-11-02 | 中国农业科学院饲料研究所 | A kind of environmental-friendly absorption zearalenone material and its application |
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| CN106890678B (en) * | 2017-03-14 | 2019-09-20 | 泰山医学院 | A kind of TiO2 magnetic bead and its application |
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| CN106984290B (en) * | 2017-06-02 | 2020-01-07 | 河南工程学院 | Preparation method of chitosan/sodium alginate magnetic composite microspheres capable of adsorbing heavy metal ions |
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| CN107583616B (en) * | 2017-09-11 | 2020-04-21 | 浙江海洋大学 | Method for adsorbing arsenic in antarctic krill oil |
| CN108176370A (en) * | 2017-12-22 | 2018-06-19 | 苏州纳贝通环境科技有限公司 | A kind of preparation method of magnetic gel heavy metal absorbent |
| CN108823187A (en) * | 2018-05-08 | 2018-11-16 | 南阳师范学院 | A kind of preparation method of cellulase and saccharomycete co-immobilization magnetic microsphere |
| CN109174027A (en) * | 2018-09-19 | 2019-01-11 | 重庆大学 | The preparation method of the fixed aluminium pillared bentonite adsorbent of sodium alginate and its method for adsorbing phosphate radical |
| CN109438732A (en) * | 2018-11-12 | 2019-03-08 | 西安交通大学 | A kind of preparation method of polyvinyl alcohol/chitosan gel rubber pearl |
| CN111036178A (en) * | 2019-12-31 | 2020-04-21 | 深圳容金科技有限公司 | Magnetic microsphere and preparation method thereof |
| CN112844328A (en) * | 2020-12-24 | 2021-05-28 | 武汉理工大学 | Sodium alginate/chitosan quaternary ammonium salt magnetic adsorption gel ball and preparation method and application thereof |
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Application publication date: 20130403 |