CN102631877A

CN102631877A - Preparation method for o-carboxymethyl chitosan hollow nanometer microspheres

Info

Publication number: CN102631877A
Application number: CN2011103866869A
Authority: CN
Inventors: 谢宇; 袁霞; 刘锦梅; 王娟; 邹志恒; 叶宝枝; 曹超文; 汪婷; 余远福
Original assignee: Nanchang Hangkong University
Current assignee: Nanchang Hangkong University
Priority date: 2011-11-29
Filing date: 2011-11-29
Publication date: 2012-08-15

Abstract

A preparation method for o-carboxymethyl chitosan hollow nanometer microspheres is characterized by including dissolving 0.3g of o-carboxymethyl chitosan into 30ml of ultrapure water; then pouring the mixture into 20ml of aqueous solution containing 0.2g of sulfonated polystyrene microspheres; continuously stirring for 2 hours; centrifugally separating; washing the aqueous solution by three times by clear water; leading prepared polystyrene-o-carboxymethyl chitosan microspheres to be sufficiently scattered into 30ml of distilled water under powerful stirring; adding 2ml (2.5%) of glutaraldehyde crosslinking shell layer o-carboxymethyl chitosan in the distilled water when the temperature is 40 DEG C; centrifugally separating after keeping the temperature constant for 2 hours; finally adding the microspheres into tetrahydrofuran and stirring for 12 hours; centrifugally separating; washing the microspheres by the tetrahydrofuran repeatedly to obtain a sample; and placing the sample into a vacuum drying oven with the temperature of 40 DEG C and drying the sample for 12 hours so as to obtain the o-carboxymethyl chitosan hollow nanometer microspheres. The preparation method has the technical advantages that the preparation method has mild reaction conditions, and is simple in production process and easy in industrial production, and the microspheres have high capacity of coordinating with metal ions and can be used for treating metal ions in sewage.

Description

A kind of preparation method of o-CMC hollow Nano microsphere

Technical field

The present invention relates to that a kind of grain is controlled, good stability, can be used as the O-CMC hollow Nano microsphere of heavy metal-polluted water treatment.

Background technology

Shitosan, chemistry β by name-(1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucose is the product of de-acetyl chitin, the straight-chain polysaccharide of being made up of Glucosamine and acetylglucosamine construction unit.Shitosan is a kind of novel natural macromolecular material; Because intramolecule contains various active functional groups such as hydroxyl, amino and glycosidic bond; It is had in fields such as environment, biological medicine, industry, agriculturals widely use, shitosan is progressively paid attention to by people and is become the research focus in nearly ten years.The Preparation of Chitosan of the present invention after with modification becomes Nano microsphere or particulate as some has the metal ion of contaminative in the absorption sewage; Be incorporated into through carboxymethyl and process the O-CMC in the chitosan molecule on the O-position; Strengthen its effect of catching to metal ion; Utilize template to prepare the O-CMC hollow Nano microsphere of spherical rule, uniform particle diameter again, to be used as the adsorbent of heavy metal ion.Because the O-CMC that synthesizes has tangible acid-resisting; Help with it as adsorbent; Improved traditional not strong drawback of the general acid resistance of chitosan-based adsorbent; And stronger by its Nano microsphere acid-resisting of preparing, can in harsh sour environment, still play the effect of good adsorbent.

Summary of the invention

The preparation method who the purpose of this invention is to provide a kind of O-CMC hollow Nano microsphere, O-CMC hollow Nano microsphere can be used as the absorption to metal ion.

The present invention realizes like this; A kind of preparation method of O-CMC hollow Nano microsphere; It is characterized in that: use the sulfonated polystyrene microballoon as template in the experiment, at first the polystyrene microsphere of preparation size homogeneous makes its surface be with a certain amount of sulfonic acid group through sulfonating reaction again; Make O-carboxymethyl chitosan glycan molecule at its surface aggregation through the electrostatic interaction between sulfonate group and the shitosan then; Through being cross-linked to form the microballoon of polystyrene-O-CMC nucleocapsid structure, dissolve the polystyrene kernel with oxolane at last, obtain the O-CMC hollow microsphere of size homogeneous.Concrete scheme does, a kind of preparation method of O-CMC hollow Nano microsphere, the O-CMC of 0.3g is dissolved in the ultra-pure water of 30ml after; Pour in the aqueous solution that 20ml contains 0.2g sulfonated polystyrene microballoon, continue to stir 2h, centrifugation; With clear water washing three times, the polystyrene of preparation-O-CMC microballoon is well dispersed in the 30ml distilled water under brute force stirs, in the time of 40 ℃; The glutaraldehyde cross-linking shell O-CMC that adds 2ml 2.5%, behind the constant temperature 2h, centrifugation; At last microballoon is added and stir 12h in the oxolane, centrifugation is repeatedly washed with oxolane; The sample that obtains places 40 ℃ vacuum drying oven to dry 12h, promptly gets O-CMC hollow Nano microsphere.

Technique effect of the present invention is: reaction condition is gentle, production technology is simple, be easy to suitability for industrialized production.The O-CMC hollow Nano microsphere that obtains has tangible acid-resisting, has stronger and ability metallic ion coordination, the metal ion in can be used for disposing of sewage.

The specific embodiment

Embodiment

The present invention is raw material with the shitosan, claims the 2g shitosan in conical flask, in the NaOH of 25ml50% solution, behind the immersion 20h.Take by weighing the 8.52g monoxone and be dissolved in the 25ml isopropyl alcohol, under agitation dropwise add in the conical flask, under room temperature, react 12h, the solution suction filtration is removed desolvate; Separate the above-mentioned thing that leaches with 100ml is water-soluble, the HCl with 1mol/L is neutralized to pH=7 with solution then, with solution centrifugal; Keep supernatant, under the stirring condition, in supernatant, add the 150ml absolute ethyl alcohol; At this moment there are a large amount of floccules to separate out, leave standstill 2h, solution centrifugal.Sediment is extracted, with ethanol sediment is washed three times under the intense agitation, obtain fibrous product, put into 80 ℃ of following dry for standby of baking oven then.

The O-CMC hollow microsphere of preparation size homogeneous:

The O-CMC of step 1: 0.3g is dissolved in the ultra-pure water of 30ml.

Step 2: 0.2g sulfonated polystyrene microballoon is well dispersed in the distilled water of 20ml under ultrasonication.Then the suspension that makes in the step 1 is slowly poured in the aqueous solution of 0.2g sulfonated polystyrene microballoon under the strong agitation of magnetic stirring apparatus, and continued to stir 2h, make the sulfonated polystyrene microballoon fully adsorb O-carboxymethyl chitosan glycan molecule.The free O-carboxymethyl chitosan glycan molecule that does not adsorb in the solution is removed in centrifugation at last, and with clear water washing three times.Polystyrene-O-CMC the microballoon of preparation is well dispersed in the 30ml distilled water under brute force stirs.Put into 40 ℃ of water bath with thermostatic control heating, treat to add 2ml (2.5%) glutaraldehyde cross-linking shell O-CMC behind the temperature stabilization.Behind the constant temperature 2h, centrifugation obtains crosslinked polystyrene-O-CMC microballoon.At last microballoon is added and stir 12h in the oxolane, make the abundant corrosion of its sulfonated polystyrene kernel, centrifugation repeatedly with the oxolane washing, is guaranteed polystyrene is removed as much as possible.The sample that obtains places 40 ℃ vacuum drying oven to dry 12h.

Attach:

The preparation process of sulfonated polystyrene (PS) microballoon is following: under nitrogen atmosphere; At first the 20g styrene monomer is joined in the redistilled water of 180ml, be warming up to 70 ℃, behind the stirring 15min; Dropping 20g is dissolved with the aqueous solution of 0.6g potassium peroxydisulfate; In temperature is to react 24h under 70 ℃ of conditions, then reactant is cooled to room temperature, can obtain white PS emulsion.Get the emulsion of the above-mentioned preparation of 20ml; Centrifugal 10min under 9000 rev/mins, washing is distributed to the solid product that obtains in the 60ml concentrated sulfuric acid then; In temperature is to react 6h under 40 ℃ of conditions; Product is centrifugalized once more, and the vacuum drying oven of putting into 40 ℃ after cleaning with redistilled water is at last dried 48h, obtains yellow sulfonated polystyrene microballoon.

Claims

1. the preparation method of an O-CMC hollow Nano microsphere is characterized in that the preparation method is: after the O-CMC of 0.3g is dissolved in the ultra-pure water of 30ml, pour in the aqueous solution that 20ml contains 0.2g sulfonated polystyrene microballoon; Continue to stir 2h, centrifugation is with clear water washing three times; Polystyrene-O-CMC the microballoon of preparation is well dispersed in the 30ml distilled water under brute force stirs, and in the time of 40 ℃, adds the glutaraldehyde cross-linking shell O-CMC of 2ml 2.5%; Behind the constant temperature 2h, centrifugation adds microballoon at last and stirs 12h in the oxolane; Centrifugation; Repeatedly with the oxolane washing, the sample that obtains places 40 ℃ vacuum drying oven to dry 12h, promptly gets O-CMC hollow Nano microsphere.