CN106220871A - A kind of modification of chitosan gel micro-ball and preparation thereof and application - Google Patents

A kind of modification of chitosan gel micro-ball and preparation thereof and application Download PDF

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CN106220871A
CN106220871A CN201610619748.9A CN201610619748A CN106220871A CN 106220871 A CN106220871 A CN 106220871A CN 201610619748 A CN201610619748 A CN 201610619748A CN 106220871 A CN106220871 A CN 106220871A
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chitosan
modification
solution
ball
acetic acid
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CN106220871B (en
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王建龙
庄淑婷
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Tsinghua University
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/20—Heavy metals or heavy metal compounds
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    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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Abstract

The present invention relates to a kind of modification of chitosan gel micro-ball and preparation thereof and application, belong to environment pollution detection technical field and field of waste water treatment.Concrete preparation method specifically includes that chitosan, 5 Cl PADAB, ethylenediaminetetraacetic acid dianhydride and a small amount of water are pressed formula II and carried out partially grafted, cross-linking reaction, and dialysis purifies, it is thus achieved that modification of chitosan solution；Then concentrated, after mixing with unmodified chitosan solution, instill balling-up in alkali liquor, be washed to neutrality, obtain modification of chitosan gel micro-ball.The modification of chitosan gel micro-ball that the present invention obtains, safety non-toxic, adsorption capacity are high, easy to detect and are easily isolated, and can be used for detection and the absorption of cobalt ion in waste water.

Description

A kind of modification of chitosan gel micro-ball and preparation thereof and application
Technical field
The present invention relates to a kind of modification of chitosan gel micro-ball and preparation thereof and application, belong to environment pollution detection technology neck Territory and field of waste water treatment.
Background technology
Chitosan is the product that the chitin natural macromolecular material of cellulose (the nature reserves be only second to) is deacetylated, gathers around There are abundant hydroxyl and amino, also have some N-acetylaminos.On the one hand, these groups make to exist in chitosan molecule substantial amounts of Intramolecular and intermolecular hydrogen bonding, cause it not dissolve in aqueous slkali, only dissolves in the mineral acids such as dilute hydrochloric acid, nitric acid and great majority have Machine acid (such as formic acid and acetic acid).On the other hand, these groups have good reactivity, can well complexing metal from Son, thus effectively remove the heavy metal in solution.Chitosan has wide material sources, nontoxic, good biocompatibility, is prone to The advantages such as biodegradation, are the most promising adsorbing materials, are widely used in fields such as medicine, food and environmental conservation.
Ethylenediaminetetraacetic acid dianhydride is the product that ethylenediaminetetraacetic acid sloughs two molecular waters, and its structural formula is as follows.According to instead Answering the height of activity, ethylenediaminetetraacetic acid dianhydride can react with containing amino-compound and hydrone successively, forms amide Key and generation carboxyl.
4-(5-Chloro-2-pyridylazo)-1,3-phenylenediamine [5-Chloro-2-[(2,4-diaminophenyl) azo] Pyridine, 5-Cl-PADAB] it is a kind of azo indicator, its structural formula is as follows.5-Cl-PADAB and metal ion In conjunction with time, the nitrogen-atoms in azo group is not only electron donor, Ye Shi chromophore simultaneously.5-Cl-PADAB as metal from Sub-Cu2+、Co2+、Ni2+Indicator, after being in contact with it, it may occur that macroscopic color change.But, current research side Overweighting spectrophotography, part research relates to titrate indicator, there are no the research being grafted in macromolecule organic.Remove Outside azo group, 5-Cl-PADAB structure also has amino, can react with carboxyl or anhydride under suitable condition, be The metal ion developer of potential grafted on high-molecular organic material.
Summary of the invention
The invention provides a kind of modification of chitosan gel micro-ball and preparation thereof and application, concrete technical scheme is as follows:
A kind of modification of chitosan, its chemical structural formula is formula I:
Described modification of chitosan is modification of chitosan gel micro-ball.
The preparation method of modification of chitosan gel micro-ball as mentioned above: chitosan, 5-Cl-PADAB and ethylenediaminetetraacetic acid Dianhydride is pressed formula II and is carried out partially grafted, cross-linking reaction, and dialysis purifies, it is thus achieved that modification of chitosan solution；Then concentrated, After being sufficiently mixed with unmodified chitosan solution, instill balling-up in alkali liquor, be washed to neutrality, obtain modification of chitosan gel micro- Ball.
Specifically include following steps:
(1) chitosan of certain mass is dissolved in aqueous acetic acid, adds a certain amount of methanol after fully dissolving molten Liquid；
(2) 5-Cl-PADAB and the ethylenediaminetetraacetic acid dianhydride of certain mass are sequentially added into solution prepared by step (1) In, it is stirred at room temperature 24-48h；
(3) step (2) gained solution deionized water is done dialysis solution, colourless to dialysis solution with bag filter dialysis, then add Enter deionized water dialysis 12-48h, it is thus achieved that pure modification of chitosan solution；
(4) solution in step (3) gained bag filter is evaporated under the conditions of 30-55 DEG C, obtain concentrated solution；
(5) adding chitosan in step (4) gained concentrated solution, and add a certain amount of aqueous acetic acid, stirring is to molten Solve completely, stand 5-10h so that bubble collapse；
(6) by step (5) gained solution, instill in NaOH solution with drops, it is thus achieved that spherical gel microsphere；Place 1- After 12h, with deionized water cyclic washing gel micro-ball so that the pH of cleaning mixture, close to neutral, obtains modification of chitosan gel micro- Ball.
In step (1), the concentration of aqueous acetic acid is 5%-15% (v/v)；The concentration ratio of chitosan and aqueous acetic acid For 2%-5% (m/v)；Methanol solution volume is 5-10 times of aqueous acetic acid volume.
In step (2), the mol ratio of ethylenediaminetetraacetic acid dianhydride and 5-Cl-PADAB is (4:1)-(1:1)；Chitosan and Ethylenediaminetetraacetic acid dianhydride mol ratio controls more than 1:1, and wherein the molal quantity of chitosan calculates with monomer.
In step (3), chitosan can be trapped in bag by selected dialyzer.
In step (4), 0.5-4 times of the aqueous acetic acid volume that the volume of concentrated solution is added by step (1).
In step (5), the concentration of aqueous acetic acid is 3%-5% (v/v), and chitosan with the concentration ratio of aqueous acetic acid is 2%-4% (m/v).
In step (6), the concentration of NaOH solution be 10%-40% (m/v), the pH of cleaning mixture be 6-7.
Modification of chitosan gel micro-ball as above application in terms of cobalt ion in detection and absorption water, it is maximum full It is 8.00～10.00mg/g with adsorbance.
Beneficial effects of the present invention is as follows:
(1) preparation method of the present invention is simple, and reaction condition is gentle, it is easy to operation, infrared detections shows, ethylenediamine tetraacetic Acetic acid dianhydride and 5-Cl-PADAB are the most successfully grafted on chitosan.
(2) present invention is on the basis of the superperformance of cobalt ion, to pass through ethylenediaminetetraacetic acid in chitosan absorption water Indicator 5-Cl-PADAB containing amino is grafted on chitosan by dianhydride, and introduces carboxyl, at inconspicuous attenuating chitosan On the basis of absorption property, increase the detection performance to cobalt ion.
(3) adsorption of modification of chitosan gel micro-ball, can make the cobalt ion in solution obtain richness on the sorbent Collection, in indicator, the developer of trace can occur obvious color to change, visually observed.
(4) the chitosan cheaper starting materials used by the present invention be easy to get, environmental friendliness, it is adaptable to industrial applications.
Accompanying drawing explanation
Fig. 1 is the FTIR figure of chitosan and modification of chitosan；
Fig. 2 is comparison diagram before and after the modification of chitosan gel micro-ball prepared of the present invention and cobalt ion absorption；Fig. 2 (a) is for inhaling Before attached, after Fig. 2 (b) is for absorption；
Fig. 3 is the adsorption capacity-time graph of modification of chitosan gel micro-ball adsorption of cobalt ion.
Detailed description of the invention
The present invention being expanded on further below in conjunction with specific embodiment, these embodiments are merely to illustrate the present invention, and do not limit The scope of the present invention processed.Additionally, after having read present disclosure, the present invention can be made various by those skilled in the art Changing or amendment, these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
0.1763g chitosan (MW:130kDa, deacetylation: 90%) is dissolved in (10%, v/ in 5mL aqueous acetic acid V), 30mL methanol, magnetic agitation 20min are added after being sufficiently stirred for dissolving.By 5-Cl-PADAB (10mg) and ethylenediaminetetraacetic acid Dianhydride (20mg) is sequentially added into wherein, at room temperature magnetic agitation 48h.Then it is 3500 by gained solution molecular cut off Bag filter dialysis 24h, change a water every 2h, until dialysis solution is colourless, add deionized water dialysis 12h, it is thus achieved that pure Modification of chitosan.Solution in bag filter in an oven 50 DEG C of environment will evaporate excessive moisture subsequently so that solution is concentrated into About 10mL.Taking 5mL concentrated solution and be dried into solid in 50 DEG C of environment, detect for FTIR, its result is as follows:
Compared with chitosan, modification of chitosan is at 1737cm-1、1634cm-1、827cm-1Increase characteristic absorption peak newly, respectively Corresponding to the C=O stretching vibration peak of carboxylic acid, the stretching vibration (amide Ⅰ) of C=O, phenyl ring 1,2,4 three replacement C-H in-CONH- The out-of-plane bending vibration of two adjacent H.The trisubstituted phenyl ring in amido link, carboxyl and 1,2,4 in chitin modified material is described Existence, just corresponding to the reaction of anhydride and amino, the reaction of anhydride and water and the part-structure of 5-Cl-PADAB.5-is described Cl-PADAB and ethylenediaminetetraacetic acid dianhydride are successfully grafted onto on chitosan.
Embodiment 2
Take the concentrated solution prepared by 5mL embodiment 1, add 0.15g chitosan, and add 0.2mL glacial acetic acid solution, stirring To being completely dissolved, and place 6h to bubble collapse.Extract this mixed liquor with 10mL syringe needle, inject with drops 100mL mass body fraction is in the NaOH solution of 15%, it is thus achieved that gel micro-ball.After placing a period of time, with deionized water not Disconnected flushing gel micro-ball so that pH value of solution is close to neutral, it is thus achieved that modification of chitosan gel micro-ball.
Embodiment 3
If taking above-mentioned modification of chitosan gel micro-ball dry granular, add 100mg/L Co2+In solution, can meat within half a minute Observe and observe: modification of chitosan gel micro-ball is become obvious pink from white.Ibid, if taking modification of chitosan gel micro-ball Dry granular respectively with containing Sn2+,Ag+,Pb2+,Sr2+,Al3+,Ce3+,Cs2+,Fe3+And Mg2+Solution reaction, without above-mentioned phenomenon.
Embodiment 4
Take the modification of chitosan gel micro-ball (moisture content is about 95%) of 0.6175g join 50mL containing Co2+In solution, Sample at set intervals, use flame atomic absorption spectrometry Co2+Concentration change.Testing result shows, Co2+Initial concentration For 95.7mg/L, adsorbing and be substantially saturated after reaction 90min, maximum saturation adsorbance is 8.00mg/g.

Claims (10)

1. a modification of chitosan, it is characterised in that chemical structural formula is formula I:
Modification of chitosan the most according to claim 1, it is characterised in that described modification of chitosan is modification of chitosan gel Microsphere.
The preparation method of modification of chitosan gel micro-ball the most according to claim 2, it is characterised in that chitosan, 5-Cl- PADAB and ethylenediaminetetraacetic acid dianhydride water carry out partially grafted, cross-linking reaction, and dialysis purifies, it is thus achieved that modification of chitosan solution；So After concentrated, after being sufficiently mixed with unmodified chitosan solution, instill balling-up in alkali liquor, be washed to neutrality, obtain modification Chitosan gel rubber microsphere.
Preparation method the most according to claim 3, it is characterised in that specifically include following steps:
(1) chitosan of certain mass is dissolved in aqueous acetic acid, after fully dissolving, adds a certain amount of methanol solution；
(2) 5-Cl-PADAB and the ethylenediaminetetraacetic acid dianhydride of certain mass are sequentially added in solution prepared by step (1), Stir certain time under room temperature；
(3) step (2) gained solution deionized water is done dialysis solution, colourless to dialysis solution with bag filter dialysis, add Ionized water is dialysed a period of time, it is thus achieved that pure modification of chitosan solution；
(4) solution in step (3) gained bag filter is evaporated at a lower temperature, obtain concentrated solution；
(5) adding chitosan in step (4) gained concentrated solution, and add a certain amount of aqueous acetic acid, stirring is to having dissolved Entirely, a period of time is stood so that bubble collapse；
(6) by step (5) gained solution, instill in NaOH solution with drops, it is thus achieved that spherical gel microsphere；When placing one section After between, with deionized water cyclic washing gel micro-ball so that the pH of cleaning mixture, close to neutral, obtains modification of chitosan gel micro- Ball.
Preparation method the most according to claim 4, it is characterised in that in step (1), the concentration of aqueous acetic acid is 5%- 15% (v/v)；The concentration of chitosan and aqueous acetic acid is than for 2%-5% (m/v)；Methanol solution volume is aqueous acetic acid body Long-pending 5-10 times；In step (5), the concentration of aqueous acetic acid is 3%-5% (v/v), chitosan and the concentration of aqueous acetic acid Ratio is 2%-4% (m/v).
Preparation method the most according to claim 4, it is characterised in that in step (2), ethylenediaminetetraacetic acid dianhydride and 5- The mol ratio of Cl-PADAB is (4:1)-(1:1)；Chitosan and ethylenediaminetetraacetic acid dianhydride mol ratio control more than 1:1, its The molal quantity of middle chitosan calculates with monomer；Mixing time is 24-48h.
Preparation method the most according to claim 4, it is characterised in that in step (4), the volume of concentrated solution is step (1) 0.5-4 times of the aqueous acetic acid volume added；Evaporation is carried out under the conditions of 30-55 DEG C.
Preparation method the most according to claim 4, it is characterised in that in step (6), the concentration of NaOH solution is 10%- 40% (m/v), the pH of cleaning mixture are 6-7；Standing time is 1-12h.
9. the application in terms of cobalt ion in detection and absorption water of the modification of chitosan gel micro-ball described in claim 2.
Application the most according to claim 9, it is characterised in that maximum saturation adsorbance is 8.00～10.00mg/g.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107056986A (en) * 2017-03-30 2017-08-18 池州学院 A kind of chitosan-based high hydroscopic resin process for cleanly preparing
CN108395730A (en) * 2018-03-20 2018-08-14 上海阿拉丁生化科技股份有限公司 A kind of synthetic method of 4- (5- Chloro-2-pyridylazos) -1,3- phenylenediamines
CN108993454A (en) * 2018-09-28 2018-12-14 武汉工程大学 A kind of preparation method of chelate sorbent
CN109248667A (en) * 2018-09-28 2019-01-22 武汉工程大学 A kind of chitosan graft object and its preparation method and application
CN111482163A (en) * 2020-04-23 2020-08-04 海南大学 Preparation method of enhanced chitosan-based aerogel for adsorbing heavy metal ions

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CN105688829A (en) * 2016-02-22 2016-06-22 清华大学 Calcium alginate/5-Cl-PADAB microspheres and preparation method and application thereof

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CN105688829A (en) * 2016-02-22 2016-06-22 清华大学 Calcium alginate/5-Cl-PADAB microspheres and preparation method and application thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107056986A (en) * 2017-03-30 2017-08-18 池州学院 A kind of chitosan-based high hydroscopic resin process for cleanly preparing
CN108395730A (en) * 2018-03-20 2018-08-14 上海阿拉丁生化科技股份有限公司 A kind of synthetic method of 4- (5- Chloro-2-pyridylazos) -1,3- phenylenediamines
CN108395730B (en) * 2018-03-20 2020-01-31 上海阿拉丁生化科技股份有限公司 Synthesis method of 4- (5-chloro-2-pyridylazo) -1, 3-phenylenediamine
CN108993454A (en) * 2018-09-28 2018-12-14 武汉工程大学 A kind of preparation method of chelate sorbent
CN109248667A (en) * 2018-09-28 2019-01-22 武汉工程大学 A kind of chitosan graft object and its preparation method and application
CN111482163A (en) * 2020-04-23 2020-08-04 海南大学 Preparation method of enhanced chitosan-based aerogel for adsorbing heavy metal ions
CN111482163B (en) * 2020-04-23 2023-04-14 海南大学 Preparation method of enhanced chitosan-based aerogel for adsorbing heavy metal ions

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