CN105061785A - Preparation method of magnetic cellulose microspheres - Google Patents
Preparation method of magnetic cellulose microspheres Download PDFInfo
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- CN105061785A CN105061785A CN201510514937.5A CN201510514937A CN105061785A CN 105061785 A CN105061785 A CN 105061785A CN 201510514937 A CN201510514937 A CN 201510514937A CN 105061785 A CN105061785 A CN 105061785A
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Abstract
The invention discloses a preparation method of magnetic cellulose microspheres. The method includes the steps that under the condition of nitrogen charge, mixed liquor of an FeC13.6H2O water solution, an FeC12.4H2O water solution and a KOH water solution is stirred and subjected to magnetic separation to prepare Fe3O4 magnetic fluid; cellulose is dissolved in ion liquid to obtain a clarified colloidal solution, and then Fe3O4 nanometer particles are added to be constantly stirred to achieve homogenization; then the mixture is dispersed in an emulsifying system composed of vacuum pump oil and polysorbate 80, so that cellulose microspheres are regenerated from the ion liquid, and then the magnetic cellulose microspheres are obtained. The preparation method has the advantages that high polymer materials generally have magnetic responsiveness due to existence of the Fe3O4 nanometer particles, and therefore the application convenience is improved; compared with traditional organic solvent, the ion liquid is environmentally-friendly solvent and can prevent pollution; by the utilization of the cheap cellulose raw materials, the magnetic cellulose microspheres serving as high-added-value products are obtained, and great economic value and social benefits are achieved.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic cellulose microsphere, belong to Material Field.
Background technology
Mierocrystalline cellulose is extensively present in occurring in nature as the natural organic polymer of one, is the natural polymer that on the earth, content is the abundantest, is also the most valuable natural reproducible resources of the mankind.Although cellulosic amount is very large, so far, have certain limitation to the research of Mierocrystalline cellulose and its derivative, it is mainly to the utilization of Mierocrystalline cellulose itself, and less to the research that cellulose conversion is become high-end product to use.
Summary of the invention
For solving the problem, the object of the invention is to: the preparation method that a kind of magnetic cellulose microsphere is provided, adding magnetic Fe
3o
4nanoparticle makes it have magnetic responsiveness, improves the convenience of its application; Compared with traditional organic solvent, ionic liquid is a kind of green solvent, can preventing pollution; High value added product magnetic cellulose microsphere can be obtained by the cellulosic material of cheapness, there is good economic worth and social benefit.
To achieve these goals, technical scheme provided by the invention is:
(1) in there-necked flask, 4-10mmolFeCl is added
36H
2the O aqueous solution and 2-6mmolFeCl
24H
2the O aqueous solution, mechanical stirring under rotating speed is 400-600r/min, adds rapidly the KOH solution of 50-100mmol, continue to stir 30-40min after the complete blackening of solution, reaction process is carried out when logical nitrogen, carries out Magneto separate, remove supernatant liquid after reaction near solution left standstill magnetic field;
Above-mentioned FeCl
36H
2the O aqueous solution, FeCl
24H
2the ion-reaction equation occurred when the mixed solution of the O aqueous solution and the KOH aqueous solution stirs is: Fe
3++ Fe
2++ 8OH
-=Fe
3o
4+ 4H
2o, generating Z 250 under this reaction conditions is magnetic metal oxide particle, at occurring in nature, the content of iron is a lot, cost is lower, is conducive to our production, is wherein to make the mixing of two kinds of dissolution homogeneity to two kinds of ferric ion solutions mechanical stirring, passing into nitrogen in reaction process is air in order to discharge in reaction process in liquor, prevents the oxygen in air and reaction reagent generation oxidizing reaction.
(2) add deionized water 40-60ml and again carry out Magneto separate after carrying out mechanical stirring 8-12min, removing supernatant liquid;
Above-mentioned magnetic separation technique is a kind of technology of material being carried out magnetic field treatment, and this technology is the difference utilizing element or component magnetic susceptibility, by foreign field, material is carried out magnetic field treatment, thus reaches a kind of emerging technology of idetified separation process.
(3) repeating step (2) carries out washing 2-3 time; By gained solid dispersal in deionized water, and ultrasonic 20-30min obtains Fe
3o
4magnetic fluid, vacuum-drying is for subsequent use;
It is to make Z 250 solid particulate be evenly distributed in water further that above-mentioned solid dispersal carries out supersound process in water, forms magnetic fluid, is conducive to follow-up experimental implementation.
(4) respectively raw cellulose and ionic liquid are placed in vacuum drying oven to process, the temperature of vacuum drying oven remains on 60-70 DEG C; By process after cellulose dissolution in process after ionic liquid in, the temperature of ionic liquid remains on 80-100 DEG C, after 20-30min obtain clarification colloidal solution, will the Fe of 1/4-1/2 Mierocrystalline cellulose quality be equivalent to
3o
4magnetic fluid adds in clarification colloidal solution, continuously stirring 20-40min, again mixing solutions is scattered in the emulsification system be made up of vacuum pump oil and tween 80, stir under 1000-2000rpm rotating speed, continue emulsification 1.5-2.5h, subsequently dehydrated alcohol is added suspension, be cooled to room temperature, suspension solidifies, with magnet, obtained microballoon is separated from solution, and respectively rinse 2-3 time with ethanol and distilled water, obtain magnetic cellulose microsphere, be placed in 2-5 DEG C of deionized water or vacuum lyophilization is preserved.
It is moisture in order to remove wherein that above-mentioned raw materials Mierocrystalline cellulose and ionic liquid are placed in vacuum drying oven, and prevent moisture to the interference effect of experiment, after Z 250 being added solution, continuously stirring is to make solution homogenization, emulsification is that a kind of liquid is evenly dispersed in the effect in immiscible another kind of liquid with atomic small droplets, vacuum pump oil wherein in emulsion has splendid oxidative stability, long-term under the high temperature conditions with air, resin, chemical feedstockss etc. directly contact also not perishable, reduce the formation of harmful paint film and grease, the longer drain period is provided, there is excellent rust resistance and corrosion resistance, very effective corrosion prevention film can be formed in metallic surface, thus the system corrosion that causes because sucking corrosive gases and moisture can be prevented comprehensively, rapidly the moisture carried secretly in fluid can be separated, reach required vacuum tightness, tool is compared with the vapour pressure at the end, prevent oil product diffusion of backflowing from the inner chamber of pump to vacuum system from causing and return oil, thus ensure enough highest attainable vacuums, tween 80 is a hydrophilic tensio-active agent, there is the effect of very strong ruptured cell film and cause pungency, hemolytic and histamine release (sensitization), this emulsification system can make Mierocrystalline cellulose, ionic liquid, Z 250 carries out emulsification under vacuum, pure magnetic cellulose microsphere can be obtained.
FeCl described above
36H
2the O aqueous solution, FeCl
24H
2the concentration of the O aqueous solution and the KOH aqueous solution is respectively 0.3-0.5mol/L, 0.1-0.3mol/L and 1-3mol/L, and this reaction is carried out under low concentration, is conducive to solution complete reaction, reduces the consumption of resource.
Above-mentioned ionic liquid is made up of organic cation and inorganic anion, organic cation is: at least one in quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazolium ion and pyrroles's salt ion, inorganic anion is: halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, can reach the object of green dissolving cellulos.As: 1-butyl-3-methyl chloride is for imidazoles, 1-butyl-3-Methylimidazole Tetrafluoroboric acid, chlorination N-N-ethyl pyrrole N-, 1-allyl group-3-Methylimidazole villaumite.
The mass ratio of above-mentioned raw materials Mierocrystalline cellulose and ionic liquid is 1:5-1:15, can ensure that Mierocrystalline cellulose is dissolved completely in ionic liquid.
Described Mierocrystalline cellulose is placed in vacuum drying oven and carries out process 40-50min, and ionic liquid is placed in vacuum drying oven respectively and carries out process 60-80min.
Compared with the existing technology comparatively, technique effect of the present invention is: abundant raw material source, and preparation method is simple, quick, with low cost, and the magnetic cellulose microsphere prepared by the method has high added value, substantially increases cellulosic economic benefit.
Embodiment
Be described in further detail the present invention below in conjunction with embodiment, wherein following examples are only for clearly illustrating technical scheme of the present invention, and can not limit the scope of the invention.The those of ordinary skill of described technical field, according to above content disclosed by the invention, all can realize object of the present invention.
Embodiment 1:
A preparation method for magnetic cellulose microsphere, comprises the following steps:
(1) in there-necked flask, add the FeCl of 0.3mol/L
36H
2the FeCl of the O aqueous solution 4mmol and 0.2mol/L
24H
2o aqueous solution 2mmol, mechanical stirring under rotating speed is 400r/min, adds rapidly the KOH solution 50mmol of 1mol/L, continue to stir 30min after the complete blackening of solution, reaction process is carried out when logical nitrogen, carries out Magneto separate, remove supernatant liquid after reaction near solution left standstill magnetic field;
(2) add deionized water 40ml and again carry out Magneto separate after carrying out mechanical stirring 8min, removing supernatant liquid;
(3) repeating step (2) carries out washing 2 times, and by gained solid dispersal in deionized water, and ultrasonic 20min obtains Fe
3o
4magnetic fluid, vacuum-drying is for subsequent use;
(4) the 1-butyl-3-methyl chloride of the raw cellulose of 7g and 98g is placed in vacuum drying oven for imidazoles to process, and control its temperature at 70 DEG C, wherein Mierocrystalline cellulose is placed in vacuum drying oven and carries out process 40min, and ionic liquid is placed in vacuum drying oven and carries out process 70min, Mierocrystalline cellulose is being dissolved in the 1-butyl-3-methyl chloride of 100 DEG C in imidazoles, is obtaining clarification colloidal solution after 30min, will the Fe of 1/2 Mierocrystalline cellulose quality be equivalent to
3o
4magnetic fluid adds in clarification colloidal solution, continuously stirring 40min, being scattered in by mixing solutions by vacuum pump oil and tween 80 is again in the emulsification system that forms of 1:1 with mass ratio, stir under 2000rpm rotating speed, continue emulsification 2.5h, subsequently dehydrated alcohol is slowly added suspension, slowly be cooled to room temperature, suspension solidification is so that magnetic cellulose microsphere regenerates from ionic liquid, with magnet, obtained microballoon is separated from solution, and respectively rinse 3 times with ethanol and distilled water, obtain pure magnetic cellulose microsphere, yield is 30%, magnetic cellulose microsphere particle diameter is not at 10-1000 micron etc.
Embodiment 2:
A preparation method for magnetic cellulose microsphere, comprises the following steps:
(1) in there-necked flask, add the FeCl of 0.44mol/L
36H
2the O aqueous solution 10mmol and 0.3mol/LFeCl
24H
2o aqueous solution 6mmol, mechanical stirring under rotating speed is 600r/min, add rapidly the KOH solution 100mmol of 3mol/L, continue to stir 40min after the complete blackening of solution, reaction process is carried out when logical nitrogen, and after having reacted, reaction solution leaves standstill near magnetic field and carries out Magneto separate, treat that solution is clarified completely, remove supernatant liquid;
(2) add deionized water 60ml and again carry out Magneto separate after carrying out mechanical stirring 12min, removing supernatant liquid;
(3) repeating step (2) carries out washing 3 times, and by gained solid dispersal in being equipped with in deionized water, and ultrasonic 30min obtains Fe
3o
4magnetic fluid, vacuum-drying is for subsequent use;
(4) the 1-butyl-3-Methylimidazole Tetrafluoroboric acid of the raw cellulose of 9g and 100g is placed in vacuum drying oven, its temperature remains on 60 DEG C, by cellulose dissolution in the ionic liquid of 80 DEG C, obtain clarification colloidal solution after 20min, will the Fe of 1/4 Mierocrystalline cellulose quality be equivalent to
3o
4magnetic fluid adds in clarification colloidal solution, continuously stirring 20min, being scattered in by mixing solutions by vacuum pump oil and tween 80 is again in the emulsification system that forms of 1:1.5 with mass ratio, stir under 1000rpm rotating speed, continue emulsification 1.5h, subsequently dehydrated alcohol is slowly added suspension, slowly be cooled to room temperature, suspension solidification is so that magnetic cellulose microsphere regenerates from ionic liquid, with magnet, obtained microballoon is separated from solution, and respectively rinse 2 times with ethanol and distilled water, obtain pure magnetic cellulose microsphere, yield is 34%, magnetic cellulose microsphere particle diameter is not at 10-1000 micron etc.
Embodiment 3:
A preparation method for magnetic cellulose microsphere, comprises the following steps:
(1) in there-necked flask, add the FeCl of 0.5mol/L
36H
2the FeCl of the O aqueous solution 6mmol and 0.1mol/L
24H
2o aqueous solution 4mmol, mechanical stirring under rotating speed is 500r/min, add rapidly the KOH solution 70mmol of 1.8mol/L, continue to stir 35min after the complete blackening of solution, reaction process is carried out when logical nitrogen, and after having reacted, reaction solution leaves standstill near magnetic field and carries out Magneto separate, treat that solution is clarified completely, remove supernatant liquid;
(2) add deionized water 50ml and again carry out Magneto separate after carrying out mechanical stirring 10min, removing supernatant liquid;
(3) repeating step (2) carries out washing 2 times, and by gained solid dispersal in being equipped with in deionized water, and ultrasonic 25min obtains Fe
3o
4magnetic fluid, vacuum-drying is for subsequent use;
(4) the chlorination N-N-ethyl pyrrole N-of the raw cellulose of 10g and 93g is placed in vacuum drying oven, its temperature remains on 65 DEG C, by cellulose dissolution in the ionic liquid of 80 DEG C, obtains clarification colloidal solution, will be equivalent to the Fe of 1/4 Mierocrystalline cellulose quality after 25min
3o
4magnetic fluid adds in solution, continuously stirring 30min, being scattered in by mixing solutions by vacuum pump oil and tween 80 is again in the emulsification system that forms of 1:3 with mass ratio, stir under 1200rpm rotating speed, continue emulsification 2h, subsequently dehydrated alcohol is slowly added suspension, slowly be cooled to room temperature, suspension solidification is so that magnetic cellulose microsphere regenerates from ionic liquid, with magnet, obtained microballoon is separated from solution, obtain pure magnetic cellulose microsphere, yield is 32%, and magnetic cellulose microsphere particle diameter is not at 10-1000 micron etc.
Embodiment 4:
A preparation method for magnetic cellulose microsphere, comprises the following steps:
(1) in there-necked flask, 4mmolFeCl is added
36H
2the O aqueous solution and 2mmolFeCl
24H
2the O aqueous solution, mechanical stirring under rotating speed is 400r/min, add rapidly the KOH solution of 50mmol, continue to stir 30min after the complete blackening of solution, reaction process is carried out when logical nitrogen, and after having reacted, reaction solution leaves standstill near magnetic field and carries out Magneto separate, treat that solution is clarified completely, remove supernatant liquid;
(2) add deionized water 40ml and again carry out Magneto separate after carrying out mechanical stirring 8min, removing supernatant liquid;
(3) repeating step (2) carries out washing 2 times, and by gained solid dispersal in being equipped with in deionized water, and ultrasonic 20min obtains Fe
3o
4magnetic fluid, vacuum-drying is for subsequent use;
(4) the 1-allyl group-3-Methylimidazole villaumite of the raw cellulose of 9g and 95g is placed in vacuum drying oven, its temperature is kept to be 60 DEG C, by cellulose dissolution in the ionic liquid of 100 DEG C, obtain clarification colloidal solution after 20min, will the Fe of 1/4 Mierocrystalline cellulose quality be equivalent to
3o
4magnetic fluid adds in clarification colloidal solution, continuously stirring 20min, being scattered in by mixing solutions by vacuum pump oil and tween 80 is again in the emulsification system that forms of 1:2 with mass ratio, stir under 1000rpm rotating speed, continue emulsification 2h, subsequently dehydrated alcohol is slowly added suspension, slowly be cooled to room temperature, suspension solidification is so that magnetic cellulose microsphere regenerates from ionic liquid, with magnet, obtained microballoon is separated from solution, and respectively rinse 2 times with ethanol and distilled water, obtain pure magnetic cellulose microsphere, yield is 28%, magnetic cellulose microsphere particle diameter is not at 10-1000 micron etc.
Claims (5)
1. a preparation method for magnetic cellulose microsphere, is characterized in that, comprises the following steps:
(1) in there-necked flask, 4-10mmolFeCl is added
36H
2the O aqueous solution and 2-6mmolFeCl
24H
2the O aqueous solution, mechanical stirring under rotating speed is 400-600r/min, adds rapidly the KOH solution of 50-100mmol, continue to stir 30-40min after the complete blackening of solution, reaction process is carried out when logical nitrogen, carries out Magneto separate, remove supernatant liquid after reaction near solution left standstill magnetic field;
(2) add deionized water 40-60ml and again carry out Magneto separate after carrying out mechanical stirring 8-12min, removing supernatant liquid;
(3) repeating step (2) carries out washing 2-3 time; By gained solid dispersal in deionized water, and ultrasonic 20-30min obtains Fe
3o
4magnetic fluid, vacuum-drying is for subsequent use;
(4) raw cellulose and ionic liquid are placed in vacuum drying oven respectively to process, its temperature remains on 60-70 DEG C; By process after cellulose dissolution in process after ionic liquid in, the temperature of ionic liquid remains on 80-100 DEG C, after 20-30min obtain clarification colloidal solution, will the Fe of 1/4-1/2 Mierocrystalline cellulose quality be equivalent to
3o
4magnetic fluid adds in clarification colloidal solution, continuously stirring 20-40min, mixing solutions is scattered in the emulsification system be made up of vacuum pump oil and tween 80 again, stirs under 1000-2000rpm rotating speed, continue emulsification 1.5-2.5h, subsequently dehydrated alcohol is added suspension, be cooled to room temperature, suspension solidifies, and is separated by obtained microballoon with magnet from solution, and respectively rinse 2-3 time with ethanol and distilled water, obtain magnetic cellulose microsphere.
2. the preparation method of magnetic cellulose microsphere according to claim 1, is characterized in that: described FeCl
36H
2the O aqueous solution, FeCl
24H
2the concentration of the O aqueous solution and the KOH aqueous solution is respectively 0.3-0.5mol/L, 0.1-0.3mol/L and 1-3mol/L.
3. the preparation method of magnetic cellulose microsphere according to claim 1, it is characterized in that: described ionic liquid is made up of organic cation and inorganic anion, organic cation is: at least one in quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazolium ion and pyrroles's salt ion, inorganic anion is: halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions.
4. the preparation method of magnetic cellulose microsphere according to claim 1, is characterized in that: the mass ratio of described raw cellulose and ionic liquid is 1:5-1:15.
5. the preparation method of magnetic cellulose microsphere according to claim 1, is characterized in that: described Mierocrystalline cellulose is placed in vacuum drying oven and carries out process 40-50min, and ionic liquid is placed in vacuum drying oven respectively and carries out process 60-80min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694032A (en) * | 2016-03-18 | 2016-06-22 | 赵守彬 | Fiber-modified magnetic composite material and preparation method thereof |
| CN108311115A (en) * | 2018-01-30 | 2018-07-24 | 中南林业科技大学 | A kind of chitosan magnetic load TiO2The preparation and its application of composite material |
| CN110605103A (en) * | 2018-06-15 | 2019-12-24 | 中国药科大学 | Method for removing heavy metal ions in large-volume sewage |
| CN111036661A (en) * | 2019-03-28 | 2020-04-21 | 红河学院 | Method for adsorbing heavy metal arsenic in soil by filling stainless steel grating with magnetic cellulose microspheres |
| CN111229170A (en) * | 2020-01-10 | 2020-06-05 | 辽宁大学 | Amino acid modified cellulose composite ferric oxide adsorbent and preparation method and application thereof |
| CN112209477A (en) * | 2020-10-13 | 2021-01-12 | 河北冀研能源科学技术研究院有限公司 | Biological magnetic fluid activity regeneration treatment method |
| CN114272907A (en) * | 2021-12-30 | 2022-04-05 | 洛阳双罗铼材料科技有限公司 | Magnetic lignocellulose nano-microsphere and application method thereof |
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| CN101274985A (en) * | 2008-05-12 | 2008-10-01 | 武汉大学 | Magnetic cellulose microsphere, preparation thereof and use thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274985A (en) * | 2008-05-12 | 2008-10-01 | 武汉大学 | Magnetic cellulose microsphere, preparation thereof and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘会茹: "纤维素溶剂体系的研究进展", 《材料导报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694032A (en) * | 2016-03-18 | 2016-06-22 | 赵守彬 | Fiber-modified magnetic composite material and preparation method thereof |
| CN108311115A (en) * | 2018-01-30 | 2018-07-24 | 中南林业科技大学 | A kind of chitosan magnetic load TiO2The preparation and its application of composite material |
| CN110605103A (en) * | 2018-06-15 | 2019-12-24 | 中国药科大学 | Method for removing heavy metal ions in large-volume sewage |
| CN111036661A (en) * | 2019-03-28 | 2020-04-21 | 红河学院 | Method for adsorbing heavy metal arsenic in soil by filling stainless steel grating with magnetic cellulose microspheres |
| CN111229170A (en) * | 2020-01-10 | 2020-06-05 | 辽宁大学 | Amino acid modified cellulose composite ferric oxide adsorbent and preparation method and application thereof |
| CN111229170B (en) * | 2020-01-10 | 2022-04-05 | 辽宁大学 | Amino acid modified cellulose composite ferric oxide adsorbent and preparation method and application thereof |
| CN112209477A (en) * | 2020-10-13 | 2021-01-12 | 河北冀研能源科学技术研究院有限公司 | Biological magnetic fluid activity regeneration treatment method |
| CN112209477B (en) * | 2020-10-13 | 2022-07-15 | 河北建投能源科学技术研究院有限公司 | Biological magnetic fluid activity regeneration treatment method |
| CN114272907A (en) * | 2021-12-30 | 2022-04-05 | 洛阳双罗铼材料科技有限公司 | Magnetic lignocellulose nano-microsphere and application method thereof |
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Application publication date: 20151118 |