CN102863655B - Chain-ball-shaped magnetic chitosan/acetate cellulose and preparation method thereof - Google Patents
Chain-ball-shaped magnetic chitosan/acetate cellulose and preparation method thereof Download PDFInfo
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- CN102863655B CN102863655B CN201210362771.6A CN201210362771A CN102863655B CN 102863655 B CN102863655 B CN 102863655B CN 201210362771 A CN201210362771 A CN 201210362771A CN 102863655 B CN102863655 B CN 102863655B
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Abstract
The invention discloses chain-ball-shaped magnetic chitosan/acetate cellulose and a preparation method thereof and relates to a multifunctional nano-composite with organic substances coating inorganic nano particles. The chain-ball-shaped magnetic chitosan/acetate cellulose is excellent in magnetic performance, high in mechanical strength and abundant in surface functional groups. The preparation method of the chain-ball-shaped magnetic chitosan/acetate cellulose includes the steps: 1) adding acetate cellulose solution into chitosan solution with stirring so that chitosan and acetate cellulose mixed solution is obtained; 2) adding hydrophilic ferrous acid manganese nano particles into the chitosan and acetate cellulose mixed solution obtained in the step 1) so as to obtain brown suspension; 3) spraying liquid nitrogen into the brown suspension obtained in the step 2) by a droplet generator so that ice-like particles are formed; and 4) placing the ice-like particles obtained in the step 3) into a freezing dryer for low-temperature vacuum drying, so that the chain-ball-shaped magnetic chitosan/acetate cellulose is obtained.
Description
Technical field
The present invention relates to a kind of multifunctional nano-composite of Coated with Organic Matter inorganic nano-particle, especially relate to a kind of uniform particle sizes, tool superparamagnetism and spherical chitosan magnetic/cellulose acetate of the chain that surface functional group enriches, physical strength is high and preparation method thereof.
Background technology
Due to the magnetic responsiveness of inorganic magnetic nanoparticle and the more function group feature of chitosan, chitosan magnetic has broad application prospects in the field such as biological medicine, environment protection.Pertinent literature (1, B.R.White, B.T.Stackhouse, J.A.Holcombe, J.Hazard.Mater.2009,161:848-853; 2, Y.C.Chang, D.H.Chen, J.Colloid Interf.Sci.2005,283:446-451; 3, Y.W.Chen, J.L.Wang, Chem.Eng.J.2011,168:286-292; 4, Li Baoqiang, Wang Yongliang, Zhou Yu. chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles [P]. publication number: CN101113022A.) report the matrix material of magnetic-particle and chitosan.But chitosan is easily degraded in an acidic solution, physical strength is low.Cellulose acetate has good physical strength, has closely similar molecular structure simultaneously, molecular chain all has great amount of hydroxy group, so the two has certain consistency and stronger hydrogen bonded with chitosan.Therefore, added by cellulose acetate in chitosan magnetic, the chitosan magnetic/cellulose acetate mixture of formation will be with a wide range of applications.
Summary of the invention
Object of the present invention aims to provide one and has superior magnetic property, and physical strength is high, and abundant spherical chitosan magnetic/cellulose acetate of chain of surface functional group and preparation method thereof.
The kernel of the spherical chitosan magnetic/cellulose acetate of described chain is magnetic manganous ferrite nano-particle, and particle diameter is 20 ~ 30nm, and shell is chitosan and cellulose acetate; The particle diameter of the spherical chitosan magnetic/cellulose acetate of described chain is 30 ~ 50 μm.Magnetic manganous ferrite nano-particle at room temperature has superparamagnetism, and surface is containing enriching hydroxyl and amino, and physical strength is high, is conducive to further application.
The preparation method of the spherical chitosan magnetic/cellulose acetate of described chain, comprises the following steps:
1) cellulose acetate solution is added in chitosan solution, stir, obtain chitosan and cellulose acetate mixing solutions;
2) in the chitosan and cellulose acetate mixing solutions of step 1) gained, add wetting ability manganous ferrite nano-particle, stir, obtain brown suspension;
3) by step 2) brown suspension of gained sprays into liquid nitrogen by droplet generator, forms ice-like particle;
4) the ice-like particle of step 3) gained is put into freeze drier, low-temperature vacuum drying, obtain the spherical chitosan magnetic/cellulose acetate of chain.
In step 1), described cellulose acetate solution can add in Glacial acetic acid formulated by cellulose acetate solid sample, and the content of cellulose acetate solid sample in cellulose acetate solution is 1 ~ 5g/L; Described chitosan solution can add 1% ~ 2%(Glacial acetic acid volume fraction by chitosan solid powder) acetum in formulated, the content of chitosan solid powder in chitosan solution is 10 ~ 30g/L; The volume ratio of described cellulose acetate solution and chitosan solution can be (1 ~ 2): 20.
In step 2) in, described manganous ferrite nano-particle can be 5 ~ 10g/L at the content of mixing solutions.
In step 4), the initial drying temperature of freeze drier can be-20 ~-30 DEG C, and time of drying can be 20 ~ 30h.
Chain obtained by the present invention spherical chitosan magnetic/cellulose acetate kernel is magnetic manganous ferrite nano-particle, and particle diameter is 20 ~ 30nm, and shell is chitosan and cellulose acetate; The particle diameter of the spherical chitosan magnetic/cellulose acetate of described chain is 30 ~ 50 μm.Magnetic manganous ferrite nano-particle at room temperature has superparamagnetism, and surface is containing enriching hydroxyl and amino, and physical strength is high, is conducive to further application.
The wetting ability manganous ferrite nano-particle that coprecipitation synthesis goes out by the present invention adds the mixing solutions of chitosan and cellulose acetate, and after droplet generator granulation, lyophilize forms the spherical chitosan magnetic/cellulose acetate of chain.Spherical chitosan magnetic/the cellulose acetate of chain obtained by the present invention has that particle is homogeneous, tool superparamagnetism, surface functional group are abundant, physical strength advantages of higher; and the method mild condition; environmentally safe, technique is simple, easily carries out large-scale production.
Accompanying drawing explanation
Fig. 1 is the optical microphotograph picture of the mixing solutions of embodiment 1 chitosan and cellulose acetate.In figure, scale is 200 μm.
Fig. 2 is the optical microphotograph picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.In figure, scale is 200 μm.
Fig. 3 is the scanning electron microscope (SEM) photograph of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.In figure, scale is 10 μm.
Fig. 4 is the X-ray energy spectrum figure of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.In figure, X-coordinate is energy (keV), and ordinate zou is relative X-photon counting.
Fig. 5 is the magnetic hysteresis loop figure of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.In figure, X-coordinate is applied field strengths H(Oe), ordinate zou is magnetization M (emu/g), and probe temperature is 300K.
Fig. 6 is the optical microphotograph picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 2.In figure, scale is 200 μm.
Fig. 7 is the optical microphotograph picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 3.In figure, scale is 200 μm.
Fig. 8 is the magnetic hysteresis loop figure of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 4.In figure, X-coordinate is applied field strengths H(Oe), ordinate zou is magnetization M (emu/g), and probe temperature is 300K.
Embodiment
Embodiment 1
(1) 0.05g cellulose acetate solid sample is added in 10mL Glacial acetic acid, form cellulose acetate solution.
(2) prepare 1.5%(volume fraction) glacial acetic acid solution, 1g chitosan solid powder is added in 50mL glacial acetic acid solution, forms chitosan solution.
(3) 1mL cellulose acetate solution is added 20mL chitosan solution, be uniformly mixed to obtain the mixing solutions of chitosan and cellulose acetate.
(4) 0.105g manganous ferrite nano-particle is added above-mentioned mixing solutions, stir to obtain uniform brown suspension.
(5) brown suspension is added droplet generator, brown suspension sprays into liquid nitrogen by droplet generator, forms ice-like particle.
(6) ice-like particle is put into freeze drier, initial lyophilize temperature is-30 DEG C, after dry 24h, obtains the spherical chitosan magnetic/cellulose acetate of chain.
Fig. 1 is the optical microphotograph picture of the mixing solutions of embodiment 1 chitosan and cellulose acetate.Can see White Flocculus by Fig. 1, this White Flocculus is the cellulose acetate of separating out.
Fig. 2 is the optical microphotograph picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.As seen from Figure 2, the chitosan magnetic/cellulose acetate of preparation is that chain is spherical, and the size uniformity of particle ball, is about 50 μm.
Fig. 3 is the scanning electron microscopic picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.As seen from Figure 3, the spherical chitosan magnetic/surface of cellulose acetate of the chain of preparation is irregular vesicular.This surface tissue is conducive to the specific surface area improving product, for the further application of product provides good basis.
Fig. 4 is the X-ray energy spectrum figure of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.As seen from Figure 4, the spherical chitosan magnetic/cellulose acetate of the chain of preparation is made up of C, Fe, Mn, O element.
Fig. 5 is the magnetic hysteresis loop figure of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 1.As seen from Figure 5, the saturation magnetization of the spherical chitosan magnetic/cellulose acetate of chain of preparation is 12emu/g, and coercive force is 0Oe, has superparamagnetism.
Embodiment 2
(1) 0.025g cellulose acetate solid sample is added in 10mL Glacial acetic acid, form cellulose acetate solution.
(2) prepare 1%(volume fraction) glacial acetic acid solution, 0.5g chitosan solid powder is added in 50mL glacial acetic acid solution, forms chitosan solution.
(3) 2mL cellulose acetate solution is added 20mL chitosan solution, be uniformly mixed to obtain the mixing solutions of chitosan and cellulose acetate.
(4) 0.110g manganous ferrite nano-particle is added above-mentioned mixing solutions, stir to obtain uniform brown suspension.
(5) brown suspension is added droplet generator, brown suspension sprays into liquid nitrogen by droplet generator, forms ice-like particle.
(6) ice-like particle is put into freeze drier, initial lyophilize temperature is-25 DEG C, after dry 20h, obtains the spherical chitosan magnetic/cellulose acetate of chain.
Fig. 6 is the optical microphotograph picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 2.As seen from Figure 6, the chitosan magnetic/cellulose acetate of preparation is that chain is spherical, and the size uniformity of particle ball, is about 50 μm.
Embodiment 3
(1) 0.01g cellulose acetate solid sample is added in 10mL Glacial acetic acid, form cellulose acetate solution.
(2) prepare 2%(volume fraction) glacial acetic acid solution, 1.5g chitosan solid powder is added in 50mL glacial acetic acid solution, forms chitosan solution.
(3) 1.5mL cellulose acetate solution is added 20mL chitosan solution, be uniformly mixed to obtain the mixing solutions of chitosan and cellulose acetate.
(4) 0.215g manganous ferrite nano-particle is added above-mentioned mixing solutions, stir to obtain uniform brown suspension.
(5) brown suspension is added droplet generator, brown suspension sprays into liquid nitrogen by droplet generator, forms ice-like particle.
(6) ice-like particle is put into freeze drier, initial lyophilize temperature is-30 DEG C, after dry 30h, obtains the spherical chitosan magnetic/cellulose acetate of chain.
Fig. 7 is the optical microphotograph picture of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 3.As seen from Figure 7, the chitosan magnetic/cellulose acetate of preparation is that chain is spherical, and the size uniformity of particle ball, is about 30 μm.
Embodiment 4
(1) 0.05g cellulose acetate solid sample is added in 10mL Glacial acetic acid, form cellulose acetate solution.
(2) prepare 2%(volume fraction) glacial acetic acid solution, 1.5g chitosan solid powder is added in 50mL glacial acetic acid solution, forms chitosan solution.
(3) 1.5mL cellulose acetate solution is added 20mL chitosan solution, be uniformly mixed to obtain the mixing solutions of chitosan and cellulose acetate.
(4) 0.15g manganous ferrite nano-particle is added above-mentioned mixing solutions, stir to obtain uniform brown suspension.
(5) brown suspension is added droplet generator, brown suspension sprays into liquid nitrogen by droplet generator, forms ice-like particle.
(6) ice-like particle is put into freeze drier, initial lyophilize temperature is-20 DEG C, after dry 30h, obtains the spherical chitosan magnetic/cellulose acetate of chain.
Fig. 8 is the magnetic hysteresis loop figure of the spherical chitosan magnetic/cellulose acetate of chain prepared by embodiment 4.As seen from Figure 8, the saturation magnetization of the spherical chitosan magnetic/cellulose acetate of chain is 14emu/g, and coercive force is 0Oe, has superparamagnetism.By changing manganous ferrite nano-particle add-on controllable gained mixture saturation magnetization.
Claims (2)
1. the spherical chitosan magnetic/cellulose acetate of chain, it is characterized in that the kernel of the spherical chitosan magnetic/cellulose acetate of described chain is magnetic manganous ferrite nano-particle, particle diameter is 20 ~ 30nm, and shell is chitosan and cellulose acetate; The particle diameter of the spherical chitosan magnetic/cellulose acetate of described chain is 30 ~ 50 μm;
Spherical chitosan magnetic/the cellulose acetate of described chain is prepared by following methods:
1) cellulose acetate solution is added in chitosan solution, stir, obtain chitosan and cellulose acetate mixing solutions; Described cellulose acetate solution adds in Glacial acetic acid formulated by cellulose acetate solid sample, and the content of cellulose acetate solid sample in cellulose acetate solution is 1 ~ 5g/L; It is formulated in the acetum of 1% ~ 2% that described chitosan solution adds Glacial acetic acid volume fraction by chitosan solid powder, and the content of chitosan solid powder in chitosan solution is 10 ~ 30g/L; The volume ratio of described cellulose acetate solution and chitosan solution is (1 ~ 2): 20;
2) in step 1) add magnetic manganous ferrite nano-particle in the chitosan of gained and cellulose acetate mixing solutions, stir, obtain brown suspension; Described manganous ferrite nano-particle is 5 ~ 10g/L at the content of mixing solutions;
3) by step 2) brown suspension of gained sprays into liquid nitrogen by droplet generator, forms ice-like particle;
4) by step 3) the ice-like particle of gained puts into freeze drier, low-temperature vacuum drying, obtains the spherical chitosan magnetic/cellulose acetate of chain.
2. the spherical chitosan magnetic/cellulose acetate of a kind of chain as claimed in claim 1, is characterized in that in step 4) in, the initial drying temperature of freeze drier is-20 ~-30 DEG C, and time of drying is 20 ~ 30h.
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| CN110559956B (en) * | 2019-09-06 | 2022-06-21 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Hollow porous cellulose microsphere and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4285819A (en) * | 1980-01-28 | 1981-08-25 | California Institute Of Technology | Functional magnetic microspheres |
| CN101029138A (en) * | 2007-02-08 | 2007-09-05 | 上海交通大学 | Production of soluble polysaccharide-based magnetic composite nano-grain |
| DE102006037702A1 (en) * | 2006-08-11 | 2008-02-14 | Müller-Schulte, Detlef, Dr. | Magnetic composites for stem cell therapy and histological diagnosis comprise magnetic and/or metallic colloids and/or bioactive substances encapsulated in polymer particles capable of binding to stem cells |
| CN102500294A (en) * | 2011-10-25 | 2012-06-20 | 厦门大学 | Preparation method of chitosan coated manganese ferrite nano-particles |
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| JPH07188062A (en) * | 1993-12-27 | 1995-07-25 | Fushimi Seiyakushiyo:Kk | Digestive tract contrast medium and its production |
| WO2005087367A1 (en) * | 2004-03-15 | 2005-09-22 | Hitachi Maxell, Ltd. | Magnetic composite particle and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4285819A (en) * | 1980-01-28 | 1981-08-25 | California Institute Of Technology | Functional magnetic microspheres |
| DE102006037702A1 (en) * | 2006-08-11 | 2008-02-14 | Müller-Schulte, Detlef, Dr. | Magnetic composites for stem cell therapy and histological diagnosis comprise magnetic and/or metallic colloids and/or bioactive substances encapsulated in polymer particles capable of binding to stem cells |
| CN101029138A (en) * | 2007-02-08 | 2007-09-05 | 上海交通大学 | Production of soluble polysaccharide-based magnetic composite nano-grain |
| CN102500294A (en) * | 2011-10-25 | 2012-06-20 | 厦门大学 | Preparation method of chitosan coated manganese ferrite nano-particles |
Non-Patent Citations (2)
| Title |
|---|
| In vitro and in vivo evaluation of mucoadhensiveness of chitosan/cellulose acetate multimicrospheres;Hui Yun Zhou, et al.;《Journal of Biomedical Materials Research Part A》;20070626;第83A卷(第4期);第1146页正文第1-3段 * |
| Magnetic cellulose–chitosan hydrogels prepared from ionic liquids as reusable adsorbent for removal of heavy metal ions;Zhen Liu, et al.;《Chemical Communications》;20120309(第59期);第7350-7352页 * |
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