CN100451060C - Chitosan/rectorite nano composite materials and method for preparing the same - Google Patents
Chitosan/rectorite nano composite materials and method for preparing the same Download PDFInfo
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- CN100451060C CN100451060C CNB200510020062XA CN200510020062A CN100451060C CN 100451060 C CN100451060 C CN 100451060C CN B200510020062X A CNB200510020062X A CN B200510020062XA CN 200510020062 A CN200510020062 A CN 200510020062A CN 100451060 C CN100451060 C CN 100451060C
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Abstract
The present invention discloses chitosan or rectorite nanometer composite materials and a preparation method used for an antimicrobial agent thereof. The elementary composition of the chitosan or rectorite nanometer composite materials is made of chitosan and rectorite and is formed by the method that a chitosan intercalation layer enters a clay layer, the preparation method is formed by the method that firstly, the natural rectorite and a modifier carry out cation exchange to obtain organic rectorite, a chitosan solution can be dropped into organic rectorite suspending liquid at twice under the condition of stirring, a reagent is precipitated by a NaOH solution, the solution is washed into a neutral solution by distilled water and dried, and then the chitosan or rectorite nanometer composite materials are formed. The nanometer composite materials combines the adsorbing and fixed functions of the clay layer for bacterium with the bacteriostasis and bactericidal functions for the chitosan; compared with pure chitosan, the antibacterial performance can be improved greatly, and simultaneously, because clay with high heat resistant performance is uniformly dispersed in a basal body of the chitosan, the heat resistant performance of the chitosan or rectorite nanometer composite materials is better than that of the chitosan.
Description
Technical field
The present invention relates to a kind of chitosan/rectorite nano composite material that is used as antiseptic-germicide and preparation method thereof.
Background technology
Chitosan is a kind of natural antiseptic-germicide, can suppress various bacteria, fungi growth, and have that sterilizing rate height, toxicity are low, the good biocompatibility advantage of no antigen again, its research and development have tempting prospect and vast market.But,, limit its application in a lot of fields because its processing difficulties, stability and thermotolerance are relatively poor.
At present, nano composite polymer/laminated silicate material receives much attention because of combining organic and structure, physics and chemical property face inorganic materials.Because nanometer size effect and strong interfacial interaction make nano composite material have excellent heat resisting and good processing properties.Simultaneously, layered silicate has bigger specific surface area, and common bacteria, mould, virus are all had fixedly adsorption of intensive.Yet natural clay itself does not often possess sterilization or bacteriostatic function.
Summary of the invention
For solving present problems of the prior art, the invention provides a kind of chitosan/rectorite nano composite material and preparation method thereof, the anti-microbial property of this chitosan/rectorite nano composite material is more excellent, heat-resisting and processing characteristics is good than pure chitosan, and the preparation method has simply effective, pollution-free, workable advantage.
The technical solution adopted in the present invention is: chitosan/rectorite nano composite material is a raw material with chitosan, rectorite leng, adopt the direct graft process of macromole solution to make, wherein the shared total weight percent of two feed composition is respectively chitosan 66.7-98%, rectorite leng 2-33.3%; Its deacetylation of wherein used chitosan is 80-97%, and molecular weight is 1.5-2.1 * 10
5, used rectorite leng is the rectorite leng that organises with the cetyl trimethylammonium bromide modification.
The preparation method of chitosan/rectorite nano composite material provided by the invention may further comprise the steps:
(1) rectorite leng is dispersed in the suspension of making 1-2% (w/v) in the distilled water, drips cetyl trimethylammonium bromide solution, be warming up to 80-95 ℃ and constant temperature 3-6h, suction filtration is used distilled water wash, until detecting with Silver Nitrate after do not have bromide anion, be dried to constant weight, promptly get organic rectorite.
(2) organic rectorite is made the suspension of 1-2% (w/v), stirring also is heated to 50-60 ℃, chitosan is dissolved in the chitosan-acetic acid solution that is made into the 0.5-1%w/v mass volume ratio in the acetum of 0.5-1.5%v/v volume ratio, stir 3-5h, after then chitosan-acetic acid solution being added drop-wise in the rectorite leng suspension reaction 1-2d, by total concn 1.5-2.5%w/v mass volume ratio preparation chitosan solution, be added drop-wise to again in the solution that is reacting, continue to stir 1-2d, use 1-2mol/L NaOH solution precipitation reactant at last, the reaction precipitation thing is washed till neutrality with distilled water, and 50-60 ℃ of drying promptly gets matrix material.
The present invention is by the direct graft process of macromole solution as shown from the above technical solution, at first the properties-correcting agent cetyl trimethylammonium bromide being inserted into accurate two-dimentional silicate clay material rectorite leng lamella chien shih clay layer struts, rely on the chitosan macromolecular chain with the interaction between the properties-correcting agent organic group again, and the shearing force that stirs is inserted into the silicate lamella with macromolecular chain lamella is further strutted, make clay reach the homodisperse of nanoscale, obtain high molecular polymer/rectorite nano composite material.This nano composite material belongs to the rectorite leng lamella and still has certain order, and chitosan is worn the intercalation type nano composite material of fork at the sheet interlayer.
Therefore, chitosan/rectorite nano composite material provided by the invention, not only combine clay layer to the absorption fixed action of bacterium and the restraining and sterilizing bacteria effect of chitosan, its anti-microbial property is compared with pure chitosan and is greatly improved, minimum inhibitory concentration is reduced to 2-30 times of pure chitosan, the antibiotic time under the same concentration prolongs greatly, and the germ resistance of this nano composite material becomes certain ratio with the content and the interlamellar spacing of rectorite leng.Simultaneously, because the clay of high heat resistance disperses in chitosan basal body uniformly, the resistance toheat of chitosan/rectorite nano composite material improves a lot than chitosan.
Embodiment
Embodiment 1: with 4g rectorite leng adding distil water 20ml, behind the homodisperse, high-speed stirring 30min obtains stable rectorite leng suspension.The 5g cetyl trimethylammonium bromide is made into 2% (w/v) aqueous solution drips in the rectorite leng suspension that is heated to 90 ℃ constant temperature 5h, suction filtration, and repeatedly wash with distilled water, until detecting no bromide anion with Silver Nitrate, under 90 ℃, be dried to constant weight, get organic rectorite.The 1g chitosan is dissolved in the chitosan-acetic acid solution that is made into 0.5% (w/v) in 1.5% (v/v) acetic acid, stir 3h, be added drop-wise in the 1g organic rectorite suspension, stirring also is heated to 55 ℃, behind the reaction 1d, by total concn 1.5% (w/v) the preparation 1g chitosan solution of final chitosan, be added drop-wise in the solution that is reacting again, continue to stir 1d.With 1mol/L NaOH precipitin reaction thing, distilled water is washed till neutrality, 50 ℃ of dryings.Promptly get matrix material.
Embodiment 2: the organic rectorite preparation method sees embodiment 1.The 1g chitosan is dissolved in the chitosan-acetic acid solution that is made into 0.8% (w/v) in 1.2% (v/v) acetic acid, stir 3.5h, be added drop-wise in the 1g organic rectorite suspension, stirring also is heated to 60 ℃, behind the reaction 1.5d, by total concn 2% (w/v) the preparation 5g chitosan solution of final chitosan, be added drop-wise in the solution that is reacting again, continue to stir 1.5d.With 1.5mol/L NaOH precipitin reaction thing, distilled water is washed till neutrality, 55 ℃ of dryings.Promptly get matrix material.
Embodiment 3: the organic rectorite preparation method sees embodiment 1.The 1g chitosan is dissolved in the chitosan-acetic acid solution that is made into 0.5% (w/v) in 1% (v/v) acetic acid, stir 4h, be added drop-wise in the 1g organic rectorite suspension, stirring also is heated to 60 ℃, behind the reaction 2d, by total concn 2.5% (w/v) the preparation 11g chitosan solution of final chitosan, be added drop-wise in the solution that is reacting again, continue to stir 1.5d.With 1mol/L NaOH precipitin reaction thing, distilled water is washed till neutrality, 50 ℃ of dryings.Promptly get matrix material.
Embodiment 4: the organic rectorite preparation method sees embodiment 1.0.5g chitosan is dissolved in the chitosan-acetic acid solution that is made into 0.5% (w/v) in 0.5% (v/v) acetic acid, stir 4.5h, be added drop-wise in the 0.5g organic rectorite suspension, stirring also is heated to 60 ℃, behind the reaction 1.5d, by total concn 2% (w/v) the preparation 9.5g chitosan solution of final chitosan, be added drop-wise in the solution that is reacting again, continue to stir 1.5d.With 1.5mol/L NaOH precipitin reaction thing, distilled water is washed till neutrality, 60 ℃ of dryings.Promptly get matrix material.
Embodiment 5: the organic rectorite preparation method sees embodiment 1.0.5g chitosan is dissolved in the chitosan-acetic acid solution that is made into 1% (w/v) in 1% (v/v) acetic acid, stir 5h, be added drop-wise in the 0.5g organic rectorite suspension, stirring also is heated to 50 ℃, behind the reaction 1d, by total concn 2% (w/v) the preparation 24.5g chitosan solution of final chitosan, be added drop-wise in the solution that is reacting again, continue to stir 2d.With 2mol/L NaOH precipitin reaction thing, distilled water is washed till neutrality, 55 ℃ of dryings.Promptly get matrix material.
Embodiment 1,2,3,4,5 products therefroms are carried out the anti-microbial property test, and test result and product layer spacing see the following form.
From table we as can be seen, the anti-microbial property of chitosan/rectorite nano composite material all improves a lot than pure chitosan, and strengthens along with the increase of the content of rectorite leng and interlamellar spacing.
Claims (3)
1, a kind of chitosan/rectorite nano composite material, it is characterized in that: chitosan/rectorite nano composite material is a raw material with chitosan, rectorite leng, adopt the direct graft process of macromole solution to make, wherein the shared total weight percent of two feed composition is respectively chitosan 66.7-98%, rectorite leng 2-33.3%, used rectorite leng is the rectorite leng that organises through cetyl trimethylammonium bromide modification gained, and the concrete steps of the direct graft process of macromole solution of employing are as follows:
(1) rectorite leng is dispersed in the suspension of making the 1-2%w/v mass volume ratio in the distilled water, drip cetyl trimethylammonium bromide solution, be warming up to 80-95 ℃ and constant temperature 3-6 hour, suction filtration, use distilled water wash, until detecting with Silver Nitrate after do not have bromide anion, be dried to constant weight, promptly get organic rectorite;
(2) organic rectorite is made for the suspension of 1-2%w/v mass volume ratio, stirring also is heated to 50-60 ℃, chitosan is dissolved in the chitosan-acetic acid solution that is made into the 0.5-1%w/v mass volume ratio in the acetum of 0.5-1.5%v/v volume ratio, stirred 3-5 hour, then chitosan-acetic acid solution is added drop-wise to and reacts after 1-2 days in the rectorite leng suspension, by total concn 1.5-2.5%w/v mass volume ratio preparation chitosan solution, be added drop-wise to again in the solution that is reacting, continue to stir 1-2 days, use 1-2mol/L NaOH solution precipitation reactant at last, the reaction precipitation thing is washed till neutrality with distilled water, and 50-60 ℃ of drying promptly gets matrix material.
2, chitosan/rectorite nano composite material according to claim 1 is characterized in that: the deacetylation of used chitosan is 80-97%, and molecular weight is 1.5 * 10
5-2.1 * 10
5
3, a kind of method for preparing the described chitosan/rectorite nano composite material of claim 1 is characterized in that adopting following steps:
(1) rectorite leng is dispersed in the suspension of making the 1-2%w/v mass volume ratio in the distilled water, drip cetyl trimethylammonium bromide solution, be warming up to 80-95 ℃ and constant temperature 3-6 hour, suction filtration, use distilled water wash, until detecting with Silver Nitrate after do not have bromide anion, be dried to constant weight, promptly get organic rectorite;
(2) organic rectorite is made for the suspension of 1-2%w/v mass volume ratio, stirring also is heated to 50-60 ℃, chitosan is dissolved in the chitosan-acetic acid solution that is made into the 0.5-1%w/v mass volume ratio in the acetum of 0.5-1.5%v/v volume ratio, stirred 3-5 hour, then chitosan-acetic acid solution is added drop-wise to and reacts after 1-2 days in the rectorite leng suspension, by total concn 1.5-2.5%w/v mass volume ratio preparation chitosan solution, be added drop-wise to again in the solution that is reacting, continue to stir 1-2 days, use 1-2mol/L NaOH solution precipitation reactant at last, the reaction precipitation thing is washed till neutrality with distilled water, and 50-60 ℃ of drying promptly gets matrix material.
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|---|---|---|---|---|
| CN101735486B (en) * | 2009-12-17 | 2012-05-09 | 华南理工大学 | carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and preparation method thereof |
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| CN103831088B (en) * | 2014-03-21 | 2016-01-27 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | The preparation method of attapulgite/rectorite/shitosan mold toxin sorbent |
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| US11192808B2 (en) * | 2016-03-17 | 2021-12-07 | Gavish-Galilee Bio Applications Ltd. | Method for production of potable water |
| CN107129206B (en) * | 2017-05-17 | 2019-12-10 | 万卓（江苏）新材料有限公司 | Soft porcelain material with ultraviolet blocking and toxic gas removing functions and preparation method thereof |
| CN108102152B (en) * | 2017-12-14 | 2020-07-28 | 华南理工大学 | Hectorite immobilized nano-silver/chitosan antibacterial composite film for food packaging and preparation method and application thereof |
| CN109893678B (en) * | 2019-02-28 | 2021-09-03 | 武汉大学 | Rectorite-chitin nanogel composite hemostatic material and preparation method thereof |
| CN112715574B (en) * | 2021-01-20 | 2023-09-26 | 张乘邦 | Environment-friendly composite antibacterial agent and preparation method thereof |
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