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CN109320662A - Preparation of magnetically imprinted cross-linked AA/AM/BA graft-esterified cyanoethyl tapioca starch microspheres and their adsorption of copper ions - Google Patents

Preparation of magnetically imprinted cross-linked AA/AM/BA graft-esterified cyanoethyl tapioca starch microspheres and their adsorption of copper ions Download PDF

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CN109320662A
CN109320662A CN201811226006.5A CN201811226006A CN109320662A CN 109320662 A CN109320662 A CN 109320662A CN 201811226006 A CN201811226006 A CN 201811226006A CN 109320662 A CN109320662 A CN 109320662A
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cyanoethyl
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tapioca
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tapioca starch
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CN109320662B (en
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李和平
柴建啟
耿恺
张淑芬
武晋雄
张俊
龚俊
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Guilin University of Technology
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a kind of preparation of magnetic blotting crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon and to the absorption of copper ion.Using tapioca as raw material, first synthesizing cross-linked type AA/AM/BA-g- xanthic acid is esterified cyanoethyl tapioca, is wrapped up ferroso-ferric oxide to obtained magnetic modified starch microspheres inside starch derivatives with AA/AM/BA grafting esterification cyanoethyl tapioca is crosslinked；The magnetic imprinted polymer with Selective adsorption is obtained with magnetic modified starch microspheres molecular engram method and metal ion crosslinked again.Adsorption of Cu2+Ionic nature test shows the microballoon adsorption capacityQ=25.96mg/g, Cu2+Removal rateR=98.11%.Product of the present invention has good space net structure, increases specific surface area, has Selective adsorption, to Cu2+Good adsorption performance.Industrial sewage purification, in terms of the higher application value of display.

Description

Magnetic blotting is crosslinked the preparation of AA/AM/BA grafting esterification cyanoethyl tapioca microballoon And the absorption to copper ion
Technical field
The present invention relates to technical field of fine, especially magnetic blotting crosslinking AA/AM/BA grafting esterification cyanoethyl wood The preparation method of sweet potato starch microballoon and in copper ion (Cu2+) absorption aspect application.
Background technique
Spherex has the netted multiplicity of space structure, large specific surface area, rough surface porous and biodegradable etc. Feature, oneself is widely used as pharmaceutical carrier, controlled release agent and heavy metal absorbent etc..However spherex because can not displacement and Separation of solid and liquid performance is poor and is restricted its application.Magnetic starch microcapsule is using starch as carrier, by embedding or inhaling Annex IV Fe 3 O or other magnetic particles and the magnetic functional polymer material of a kind of tool formed.With spherex phase Than magnetic starch microcapsule has the advantages that the displacement under external magnetic field condition and is quickly separated by solid-liquid separation.However magnetic starch Microsphere surface functional group polarity is weaker, type is single, is difficult the processing suitable for the complicated waste water containing multiple pollutant, urgently It need to be modified to form the magnetic polymer material containing multi-functional group.
Due to composite modified the advantages of having gathered a variety of single converted starches of starch, the present invention uses esterification, connects Branch and crosslinking carry out it composite modified.Converted starch makes separation be easy to carry out after having magnetism, recycles also more convenient. Currently, the report about ion imprinted polymer largely concentrates on heavy metal template ion and its application in the treatment of waste water. Ionic imprinting technique, which is introduced into magnetic composite not only, can retain its highly selective and high identity to target substrates Characteristic, can also impart to its superparamagnetism, the expansion for the separation of material, recycling and application provides possibility.
The present invention is using tapioca as primary raw material, in synthesizing cross-linked type AA/AM/BA-g- xanthic acid esterification cyanoethyl wood On the basis of sweet potato starch, cyanoethyl tapioca is esterified by ferroso-ferric oxide packet with crosslinking AA/AM/BA grafting in anti-newborn phase solution It wraps up in and magnetic modified starch microspheres is made inside starch derivatives；Again using magnetic modified starch microspheres as functional material, molecule is used Immunoblot method further obtains the magnetic imprinted polymer with Selective adsorption with metal ion crosslinked.Products therefrom is to gold Belonging to selective absorption, desorption, regeneration and recycling of ion etc. has certain application value.
Summary of the invention
The purpose of the invention is to enhance cross-linking type BA/AA/AM-g- xanthic acid esterification cyanoethyl tapioca to metal The adsorption effect of ion, provide magnetic blotting crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon preparation method with And copper ion (Cu2+) absorption aspect application.
Specific steps of the invention are as follows:
(1) 5g tapioca is placed in 60 DEG C of vacuum constant temperature drying boxes dry 24 hours to constant weight, obtains butt para arrowroot Powder.
(2) it takes butt tapioca obtained by 4g step (1) in 250mL four-hole boiling flask, is added 12mL distilled water, and by four Mouth flask, which is placed in 50 DEG C of thermostat water bath, is made into uniform starch emulsion.
(3) 0.03g sodium hydroxide is weighed respectively and 0.2g anhydrous sodium sulfate is dissolved in 5mL distilled water, 15 points under stiring It is added in starch emulsion obtained by step (2) in clock, stir-activating 30 minutes, 2mL is then added and analyzes pure acrylonitrile, the reaction was continued 5 hours.
It (4) is 95% ethanol washing 3 times by the 15mL volume fraction of reaction solution obtained by step (3), then with the anhydrous second of 15mL Alcohol washs 3 times, filters to obtain filter cake.
(5) filter cake obtained by step (4) is put into surface plate, is placed in 60 DEG C of baking ovens dry 12 hours to constant weight, obtains cyanogen Ethyl tapioca.
(6) it takes the resulting cyanoethyl tapioca of 4g step (5) in another four-hole boiling flask, 12mL distilled water is added and prepares At cyanoethyl tapioca solution.
(7) taking 1.0mL mass fraction is that 10% sodium hydroxide solution is added in step (6) solution, stirs lower 30 points of activation Clock.
(8) 2mL pure carbon disulfide is analyzed to rapidly join in step (7) reaction system, control 30 DEG C of temperature, under stirring into Row esterification 2 hours.
(9) 0.5g magnesium sulfate, 9.5mL distilled water are taken, is dissolved in 50mL small beaker, is subsequently poured into step (8) material and increases Add the stability of product, the reaction was continued 10 minutes, obtains esterification cyanoethyl tapioca solution.
(10) 0.12g ammonium persulfate and 0.24g sodium hydrogensulfite are weighed in 50mL beaker, the stirring of 5mL distilled water is added Uniformly, initiator solution is obtained.
(11) step (9) resulting material is warming up to 50 DEG C, and pipettes initiator solution obtained by 1.5mL step (10), stirred It mixes 10 minutes.
(12) 2g analysis pure acrylic acid, 1g analysis pure acrylic acid butyl ester are weighed respectively, and 0.5g acrylamide monomer is in 50mL In small beaker, 7mL is added and analyzes pure acetone, is uniformly mixed to obtain monomer mixed solution, pours into 100mL constant pressure funnel It is spare.Remaining initiator solution in step (11) is poured into again spare in another 100mL constant pressure funnel.
(13) monomer mixed solution obtained by step (12) and initiator solution are slowly added dropwise simultaneously, control time for adding is small 3 When synchronize and be added dropwise.
(14) after being added dropwise into step (13) resulting material be added 0.08g N, N '-methylene-bisacrylamide, after Continuous reaction 2 hours, graft reaction terminates.
(15) after reaction to be done, step (14) products therefrom is filtered into obtain filter cake, and successively with 20mL distilled water, 20mL dehydrated alcohol and 10mL analysis pure acetone wash 3 times, and filter cake is put into surface plate, is placed in 50 DEG C of vacuum ovens and does To constant weight, cross-linking type xanthic acid esterification quaternary graft cyanoethyl tapioca crude product cross-linking type BA/AA/AM- is obtained within dry 24 hours G- xanthic acid is esterified cyanoethyl tapioca.
(16) crude product obtained by step (15) is placed in Soxhlet extractor, it is small with 120mL analysis pure acetone extracting 24 When, the material after taking out extracting is put into surface plate, is placed in 50 DEG C of vacuum ovens dry 12 hours to constant weight up to cross-linking type BA/AA/AM-g- xanthic acid is esterified cyanoethyl tapioca.
(17) 160mL chemistry neat liquid paraffin is added in 500mL four-hole boiling flask, is placed in 60 DEG C of stirred in water bath, then Sequentially add the pure Span 80 of 0.5g chemistry, the pure polysorbate60 of 0.5g chemistry, stirring and emulsifying 20~30 minutes.
(18) the esterification cyanoethyl tapioca of cross-linking type BA/AA/AM-g- xanthic acid obtained by 2~2.5g step (16) is taken to set In 100mL beaker, 20~25mL distilled water is added, adjusts pH with the sodium hydroxide solution of 0.2~0.5mL mass fraction 20% It is 10~11, is added in step (17) material.
(19) 0.4~0.5g ferroso-ferric oxide is weighed, 1~1.2mL analysis pure epoxy chloropropane sequentially adds step (18) In gained system, continue to be stirred to react 4~6 hours at 50~60 DEG C.The ethyl alcohol of the volume fraction 95% of 20~40mL is added Demulsification is put in dark place and stands 12 hours, and suction filtration separates to obtain grey black filter cake, successively with 20~30mL distilled water and 20~30mL Dehydrated alcohol alternately washing, suction filtration 2~3 times, then filter cake is put into surface plate, it is small that dry 24 are placed in 50 DEG C of vacuum ovens When to get magnetism crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon.
(20) the crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon of magnetism made from 2g step (20) is taken to be added In 250mL four-hole boiling flask, the copper-bath of the 0.05mol/L of 50mL is added, flask is placed in supersonic wave cleaning machine and is surpassed Sound disperses 30 minutes.
(21) after being uniformly dispersed, it is molten that the NaOH that 2~4mL mass fraction is 10% is added in the flask in step (20) Liquid, adjusting pH is 10~11, and flask is put into 50 DEG C of water-baths and is quickly stirred, and 1.2mL is then added and analyzes pure epoxy chlorine third Alkane continues stirring 5 hours.
(22) after the reaction was completed, mixed liquor obtained by step (21) is poured into beaker, and respectively with 20~30mL distilled water It washs 3~4 times with 20~30mL dehydrated alcohol, then with the oscillation of 20~30mL 0.1mol/L EDTA solution desorption 1 hour, uses Water washing is until no copper ion detects.Product is finally put into 50 DEG C of vacuum drying ovens dry 24 hours to get magnetism Imprinted crosslinked AA/AM/BA grafting esterification cyanoethyl tapioca microballoon.
(23) using the JDM-13 type vibrating specimen magnetometer of Jilin University's production at normal temperature to mesh obtained by step (22) The magnetic property of mark product magnetic blotting crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon is measured.Method is such as Under: the sample to be tested for weighing up quality is packed into specimen cup and is placed on specimen holder, specific magnetization-magnetic field of point-to-point measurement sample is closed It is that magnetic field (is first added to positive maximum, maximum is reversely added to after falling back on zero, be then added to positive maximum, it is bent to form closure by curve Line), specific saturation magnetization is obtained by hysteresis loop figure.
(24) to the crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca of target product magnetic blotting obtained by step (22) Microballoon carries out Adsorption of Cu2+Ionic nature test, the method is as follows: preparing pH is 6, and initial concentration is the Cu of 635mg/L2+Standard is molten Liquid.Take the 25mL Cu2+Standard solution is in 100mL conical flask and starch derivatives microballoon prepared by 0.6g is added, at 35 DEG C After being shaken 2 hours in constant temperature oscillator, filtered with the middling speed qualitative filter paper that aperture is 30~50 μm.Take filtrate with it is ultraviolet-can See spectrophotometry measurement wherein Cu2+Mass concentration.Cu after taking supernatant liquor measurement to adsorb after filtering2+Concentration of metal ions. Adsorption capacity Q and metal ion removal rate R (%) is calculated according to the following formula:
In formula
Q --- adsorption capacity, unit mgg-1；
R --- removal rate, %；
C0--- the initial concentration of metal ion, unit mgL-1；
Ct--- the equilibrium concentration of metal ion, unit mgL-1；
The volume of V --- adsorbent solution, unit L；
The dosage of m --- adsorbent, unit g；
Clear superiority possessed by the present invention is: magnetic blotting crosslinking AA/AM/BA grafting esterification cyanogen prepared by the present invention Ethyl tapioca microballoon had not only had the advantages that the multi-functional group that contains of composite modified starch, but also with magnetic starch microcapsule Displacement and quick the advantages of being separated by solid-liquid separation under external magnetic field condition.To Cu2+The adsorption effect of ion is excellent, repeats It utilizes, not will cause secondary pollution.
Detailed description of the invention
Fig. 1 is the SEM photograph of log sweet potato starch.
Fig. 2 is the SEM photo of magnetic blotting crosslinking crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon.
Fig. 3 is log sweet potato starch IR figure.
Fig. 4 is magnetic blotting crosslinking crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon IR figure.
Fig. 5 is the XRD diagram of log sweet potato starch.
Fig. 6 is magnetic blotting crosslinking crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon XRD figure.
Fig. 7 is TG the and DTG curve of log sweet potato starch.
Fig. 8 is the TG-DTG curve of magnetic blotting crosslinking crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon.
Fig. 9 is the hysteresis loop that magnetic blotting is crosslinked AA/AM/BA grafting esterification cyanoethyl tapioca microballoon
Specific embodiment
Embodiment:
(1) 5g tapioca is placed in 60 DEG C of vacuum constant temperature drying boxes dry 24 hours to constant weight, obtains butt para arrowroot Powder.
(2) it takes butt tapioca obtained by 4g step (1) in 250mL four-hole boiling flask, is added 12mL distilled water, and by four Mouth flask, which is placed in 50 DEG C of thermostat water bath, is made into uniform starch emulsion.
(3) 0.03g sodium hydroxide is weighed respectively and 0.2g anhydrous sodium sulfate is dissolved in 5mL distilled water, 15 points under stiring It is added in starch emulsion obtained by step (2) in clock, stir-activating 30 minutes, 2mL is then added and analyzes pure acrylonitrile, the reaction was continued 5 hours.
It (4) is 95% ethanol washing 3 times by the 15mL volume fraction of reaction solution obtained by step (3), then with the anhydrous second of 15mL Alcohol washs 3 times, filters to obtain filter cake.
(5) filter cake obtained by step (4) is put into surface plate, is placed in 60 DEG C of baking ovens dry 12 hours to constant weight, obtains cyanogen Ethyl tapioca.
(6) it takes the resulting cyanoethyl tapioca of 4g step (5) in another four-hole boiling flask, 12mL distilled water is added and prepares At cyanoethyl tapioca solution.
(7) taking 1.0mL mass fraction is that 10% sodium hydroxide solution is added in step (6) solution, stirs lower 30 points of activation Clock.
(8) 2mL pure carbon disulfide is analyzed to rapidly join in step (7) reaction system, control 30 DEG C of temperature, under stirring into Row esterification 2 hours.
(9) 0.5g magnesium sulfate, 9.5mL distilled water are taken, is dissolved in 50mL small beaker, is subsequently poured into step (8) material and increases Add the stability of product, the reaction was continued 10 minutes, obtains esterification cyanoethyl tapioca solution.
(10) 0.12g ammonium persulfate and 0.24g sodium hydrogensulfite are weighed in 50mL beaker, the stirring of 5mL distilled water is added Uniformly, initiator solution is obtained.
(11) step (9) resulting material is warming up to 50 DEG C, and pipettes initiator solution obtained by 1.5mL step (10), stirred It mixes 10 minutes.
(12) 2g analysis pure acrylic acid, 1g analysis pure acrylic acid butyl ester are weighed respectively, and 0.5g acrylamide monomer is in 50mL In small beaker, 7mL is added and analyzes pure acetone, is uniformly mixed to obtain monomer mixed solution, pours into 100mL constant pressure funnel It is spare.Remaining initiator solution in step (11) is poured into again spare in another 100mL constant pressure funnel.
(13) monomer mixed solution obtained by step (12) and initiator solution are slowly added dropwise simultaneously, control time for adding is small 3 When synchronize and be added dropwise.
(14) after being added dropwise into step (13) resulting material be added 0.08g N, N '-methylene-bisacrylamide, after Continuous reaction 2 hours, graft reaction terminates.
(15) after reaction to be done, step (14) products therefrom is filtered into obtain filter cake, and successively with 20mL distilled water, 20mL dehydrated alcohol and 10mL analysis pure acetone wash 3 times, and filter cake is put into surface plate, is placed in 50 DEG C of vacuum ovens and does To constant weight, cross-linking type xanthic acid esterification quaternary graft cyanoethyl tapioca crude product cross-linking type BA/AA/AM- is obtained within dry 24 hours G- xanthic acid is esterified cyanoethyl tapioca.
(16) crude product obtained by step (15) is placed in Soxhlet extractor, it is small with 120mL analysis pure acetone extracting 24 When, the material after taking out extracting is put into surface plate, is placed in 50 DEG C of vacuum ovens dry 12 hours to constant weight up to cross-linking type BA/AA/AM-g- xanthic acid is esterified cyanoethyl tapioca.
(17) 160mL chemistry neat liquid paraffin is added in 500mL four-hole boiling flask, is placed in 60 DEG C of stirred in water bath, then Sequentially add the pure Span 80 of 0.5g chemistry, the pure polysorbate60 of 0.5g chemistry, stirring and emulsifying 30 minutes.
(18) the esterification cyanoethyl tapioca of cross-linking type BA/AA/AM-g- xanthic acid obtained by 2g step (16) is taken to be placed in In 100mL beaker, 2mL distilled water is added, adjusting pH with the sodium hydroxide solution of 0.3mL mass fraction 20% is 11, is added to In step (17) material.
(19) 0.4g ferroso-ferric oxide is weighed, 1mL analysis pure epoxy chloropropane sequentially adds in system obtained by step (18), Continue to be stirred to react 4 hours at 50 DEG C.The ethyl alcohol demulsification of the volume fraction 95% of 20mL is added, it is small to be put in dark place standing 12 When, suction filtration separates to obtain grey black filter cake, is successively alternately washed, is filtered 3 times with 20mL distilled water and 20mL dehydrated alcohol, then will Filter cake is put into surface plate, is placed in 50 DEG C of vacuum ovens dry 24 hours to get magnetism crosslinking AA/AM/BA grafting esterification cyanogen Ethyl tapioca microballoon.
(20) the crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon of magnetism made from 2g step (19) is taken to be added In 250mL four-hole boiling flask, the copper-bath of the 0.05mol/L of 50mL is added, flask is placed in supersonic wave cleaning machine and is surpassed Sound disperses 30 minutes.
(21) after being uniformly dispersed, the NaOH solution that 3mL mass fraction is 10% is added in the flask in step (20), Adjusting pH is 10~11, and flask is put into 50 DEG C of water-baths and is quickly stirred, and 1.2mL is then added and analyzes pure epoxy chloropropane, Continue stirring 5 hours.
(22) after the reaction was completed, mixed liquor obtained by step (21) is poured into beaker, and respectively with 25mL distilled water and 25mL dehydrated alcohol washs 3 times, then with the oscillation of 25mL 0.1mol/L EDTA solution desorption 1 hour, is washed with water to no copper Until ion detects.Finally product is put into 50 DEG C of vacuum drying ovens dry 24 hours and is crosslinked AA/ to get magnetic blotting AM/BA grafting esterification cyanoethyl tapioca microballoon.
(23) 25 DEG C of magnetics imprinted crosslinked AA/AM/BA grafting esterification cyanoethyl tapioca microsphere vibration range- Between 6000~6000Oe, specific saturation magnetization 22.46emu/g.
(24) magnetic blotting crosslinking AA/AM/BA grafting esterification cyanoethyl tapioca microballoon is to Cu2+The adsorption capacity of ion Q=25.96mg/g, Cu2+Removal rate R=98.11%.
Product is analyzed through IR, in 570~590cm-1For the stretching vibration absworption peak of Fe-O, illustrate Fe3O4It wraps up successfully. Through TG and DTG map analysis, thermal stability is changed.By the SEM map analysis comparison of product and log sweet potato starch it is found that producing Object is spherical in shape, and rough surface, hole increases.XRD diagram is wrapped in product analysis shows that the crystal structure of log sweet potato starch is destroyed The Fe wrapped up in3O4Crystalline structure is constant.Product is analyzed through VSM, shows that synthesized magnetic blotting spherex has superparamagnetism.

Claims (2)

1.一种磁性印迹交联AA/AM/BA接枝酯化氰乙基木薯淀粉微球的制备方法，其特征在于具体步骤为：1. a preparation method of magnetic imprinting cross-linked AA/AM/BA graft esterification cyanoethyl tapioca starch microspheres, is characterized in that concrete steps are: (1)将5g木薯淀粉置于60℃真空恒温干燥箱中干燥24小时至恒重，得干基木薯淀粉；(1) 5g tapioca starch is placed in 60 ℃ of vacuum constant temperature drying ovens and dried to constant weight for 24 hours to obtain dry base tapioca starch; (2)取4g步骤(1)所得干基木薯淀粉于250mL四口烧瓶中，加入12mL蒸馏水，并将四口烧瓶置于50℃的恒温水浴锅中配成均匀的淀粉乳液；(2) get 4g of step (1) gained dry base tapioca starch in a 250mL four-necked flask, add 12mL of distilled water, and place the four-necked flask in a 50°C constant temperature water bath to prepare a uniform starch emulsion; (3)分别称取0.03g氢氧化钠及0.2g无水硫酸钠溶于5mL蒸馏水中，在搅拌下15分钟内加入步骤(2)所得淀粉乳液中，搅拌活化30分钟，然后加入2mL分析纯丙烯腈，继续反应5小时；(3) Weigh 0.03g of sodium hydroxide and 0.2g of anhydrous sodium sulfate and dissolve them in 5mL of distilled water respectively, add to the starch emulsion obtained in step (2) within 15 minutes under stirring, stir and activate for 30 minutes, and then add 2mL of analytical pure Acrylonitrile continued to react for 5 hours; (4)将步骤(3)所得反应液用15mL体积分数为95％乙醇洗涤3次，再用15mL无水乙醇洗涤3次，抽滤得滤饼；(4) washing the reaction solution obtained in step (3) with 15 mL volume fraction of 95% ethanol for 3 times, then washing with 15 mL absolute ethanol for 3 times, and suction filtration to obtain a filter cake; (5)将步骤(4)所得滤饼放入表面皿中，置于60℃烘箱中干燥12小时至恒重，得氰乙基木薯淀粉；(5) put the filter cake obtained in step (4) into a watch glass, and place it in a 60° C. oven to dry to constant weight for 12 hours to obtain cyanoethyl tapioca; (6)取4g步骤(5)所得的氰乙基木薯淀粉于另一四口烧瓶中，加入12mL蒸馏水配制成氰乙基木薯淀粉溶液；(6) get the cyanoethyl tapioca starch of 4g step (5) gained in another four-necked flask, add 12mL distilled water and be mixed with cyanoethyl tapioca starch solution; (7)取1.0mL质量分数为10％氢氧化钠溶液加入步骤(6)溶液中，搅拌下活化30分钟；(7) take 1.0 mL mass fraction of 10% sodium hydroxide solution and add it to the solution in step (6), and activate under stirring for 30 minutes; (8)将2mL分析纯二硫化碳快速加入步骤(7)反应体系中，控制温度30℃，搅拌下进行酯化反应2小时；(8) 2 mL of analytically pure carbon disulfide was rapidly added to the reaction system of step (7), the temperature was controlled to 30°C, and the esterification reaction was carried out under stirring for 2 hours; (9)取0.5g硫酸镁、9.5mL蒸馏水，溶于50mL小烧杯中，然后倒入步骤(8)物料中增加产品的稳定性，继续反应10分钟，得到酯化氰乙基木薯淀粉溶液；(9) get 0.5g magnesium sulfate, 9.5mL distilled water, be dissolved in 50mL small beaker, then pour into step (8) material to increase the stability of product, continue to react for 10 minutes, obtain esterified cyanoethyl tapioca starch solution; (10)称量0.12g过硫酸铵和0.24g亚硫酸氢钠于50mL烧杯中，加入5mL蒸馏水搅拌均匀，得引发剂溶液；(10) Weigh 0.12g of ammonium persulfate and 0.24g of sodium bisulfite in a 50mL beaker, add 5mL of distilled water and stir to obtain an initiator solution; (11)将步骤(9)所得物料升温至50℃，并移取1.5mL步骤(10)所得引发剂溶液，搅拌10分钟；(11) heating the material obtained in step (9) to 50°C, and pipetting 1.5 mL of the initiator solution obtained in step (10), stirring for 10 minutes; (12)分别称取2g分析纯丙烯酸、1g分析纯丙烯酸丁酯，0.5g丙烯酰胺单体于50mL小烧杯中，加入7mL分析纯丙酮，搅拌混合均匀得单体混合液，倒入100mL恒压滴液漏斗内备用；再将步骤(11)中剩余的引发剂溶液倒入另一100mL恒压滴液漏斗内备用；(12) Weigh 2g of analytically pure acrylic acid, 1g of analytically pure butyl acrylate, and 0.5g of acrylamide monomer into a 50mL small beaker, add 7mL of analytically pure acetone, stir and mix evenly to obtain a monomer mixture, pour into 100mL of constant pressure In the dropping funnel for subsequent use; pour the remaining initiator solution in the step (11) into another 100mL constant pressure dropping funnel for subsequent use; (13)同时缓慢滴加步骤(12)所得单体混合液与引发剂溶液，控制滴加时间在3小时同步滴加完毕；(13) slowly dripping step (12) gained monomer mixed solution and initiator solution simultaneously, and control the time for dripping to finish synchronously dripping in 3 hours; (14)滴加完毕后向步骤(13)所得物料中加入0.08g N,N′-亚甲基双丙烯酰胺，继续反应2小时，接枝反应结束；(14) add 0.08g N,N'-methylenebisacrylamide to the material obtained in step (13) after the completion of the dropwise addition, continue to react for 2 hours, and the grafting reaction ends; (15)待完成反应以后，将步骤(14)所得产物抽滤得滤饼，并依次用20mL蒸馏水、20mL无水乙醇和10mL分析纯丙酮洗涤3次，把滤饼放入表面皿中，置于50℃真空干燥箱中干燥24小时至恒重，得交联型黄原酸酯化四元接枝氰乙基木薯淀粉粗产物交联型BA/AA/AM- g-黄原酸酯化氰乙基木薯淀粉；(15) After the reaction is completed, the product obtained in step (14) is subjected to suction filtration to obtain a filter cake, and washed 3 times with 20 mL of distilled water, 20 mL of absolute ethanol and 10 mL of analytical acetone in turn, and the filter cake is placed in a watch glass. Dry in a vacuum drying oven at 50 °C for 24 hours to constant weight to obtain cross-linked xanthate esterified quaternary grafted cyanoethyl tapioca crude product cross-linked BA/AA/AM-g-xanthogen esterified Cyanoethyl tapioca starch; (16)将步骤(15)所得粗产物置于索氏抽提器内，用120mL分析纯丙酮抽提24小时，取出抽提后的物料放入表面皿，置于50℃真空干燥箱中干燥12小时至恒重即得交联型BA/AA/AM-g-黄原酸酯化氰乙基木薯淀粉；(16) place the crude product obtained in step (15) in a Soxhlet extractor, extract with 120 mL of analytical acetone for 24 hours, take out the extracted material and put it into a watch glass, and place it in a 50°C vacuum drying oven to dry 12 hours to constant weight to obtain cross-linked BA/AA/AM-g-xanthogenated cyanoethyl tapioca starch; (17)将160mL化学纯液体石蜡加入500mL四口烧瓶内，置于60℃水浴中搅拌，然后依次加入0.5g 化学纯Span 80、0.5g化学纯吐温60，搅拌乳化20~30分钟；(17) 160mL of chemically pure liquid paraffin was added to a 500mL four-necked flask, placed in a 60°C water bath and stirred, then 0.5g of chemically pure Span 80 and 0.5g of chemically pure Tween 60 were added successively, and the mixture was stirred and emulsified for 20 to 30 minutes; (18)取2~2.5g步骤(16)所得交联型BA/AA/AM-g-黄原酸酯化氰乙基木薯淀粉置于100mL烧杯中，加入20~25mL蒸馏水，用0.2~0.5mL质量分数20%的氢氧化钠溶液调节pH为10~11，加入到步骤(17)物料中；(18) Take 2~2.5g of the cross-linked BA/AA/AM-g-xanthogenated cyanoethyl tapioca starch obtained in step (16) and place it in a 100mL beaker, add 20~25mL of distilled water, and use 0.2~0.5mL of distilled water. The pH of 20% sodium hydroxide solution in mL mass fraction is adjusted to 10~11, and added to the material in step (17); (19)称取0.4~0.5g四氧化三铁，1~1.2mL分析纯环氧氯丙烷依次加入步骤(18)所得体系中，在50~60℃下继续搅拌反应4~6小时；加入20~40mL的体积分数95%的乙醇破乳，放于暗处静置12小时，抽滤分离得灰黑色滤饼，依次用20~30mL蒸馏水和20~30mL无水乙醇交替洗涤、抽滤2~3次，再将滤饼放入表面皿，置于50℃真空干燥箱中干燥24小时，即得磁性交联AA/AM/BA接枝酯化氰乙基木薯淀粉微球；(19) weigh 0.4～0.5g ferric oxide, 1～1.2mL analytical pure epichlorohydrin is added successively in step (18) gained system, at 50～60 ℃, continue stirring reaction 4～6 hours; Add 20 ~40mL of 95% ethanol demulsification, placed in a dark place for 12 hours, suction filtration to separate a gray-black filter cake, alternately washed with 20~30mL distilled water and 20~30mL absolute ethanol, and suction filtered for 2~ 3 times, then put the filter cake into a watch glass, and place it in a vacuum drying oven at 50 ° C to dry for 24 hours to obtain magnetic cross-linked AA/AM/BA graft-esterified cyanoethyl tapioca starch microspheres; (20)取2g步骤(20)制得的磁性交联AA/AM/BA接枝酯化氰乙基木薯淀粉微球加入250mL四口烧瓶中，再加入50mL的0.05mol/L的硫酸铜溶液，将烧瓶放在超声波清洗机内超声分散30分钟；(20) Take 2g of magnetic cross-linked AA/AM/BA graft-esterified cyanoethyl tapioca starch microspheres obtained in step (20) and add it to a 250mL four-necked flask, and then add 50mL of 0.05mol/L copper sulfate solution , put the flask in the ultrasonic cleaner for ultrasonic dispersion for 30 minutes; (21)待分散均匀后，向步骤(20)中的烧瓶加入2~4mL质量分数为10%的NaOH溶液，调节pH为10~11，并把烧瓶放到50℃水浴中快速搅拌，然后加入1.2mL分析纯环氧氯丙烷，继续搅拌5小时；(21) After dispersing evenly, add 2-4 mL of NaOH solution with a mass fraction of 10% to the flask in step (20), adjust the pH to 10-11, and put the flask in a 50°C water bath for rapid stirring, and then add 1.2mL of analytically pure epichlorohydrin, continue to stir for 5 hours; (22) 反应完成后，将步骤(21)所得混合液倒入烧杯中，并分别用20~30mL蒸馏水和20~30mL无水乙醇洗涤3~4次，然后用20~30mL 0.1mol/L EDTA溶液振荡解吸1小时，用水洗涤至无铜离子检出为止；最后把产物放入50℃恒温真空干燥箱干燥24小时，即得磁性印迹交联AA/AM/BA接枝酯化氰乙基木薯淀粉微球。(22) After the reaction is completed, pour the mixed solution obtained in step (21) into a beaker, and wash 3 to 4 times with 20 to 30 mL of distilled water and 20 to 30 mL of absolute ethanol, and then use 20 to 30 mL of 0.1 mol/L EDTA. The solution was shaken and desorbed for 1 hour, washed with water until no copper ions were detected; finally, the product was dried in a constant temperature vacuum drying oven at 50°C for 24 hours to obtain magnetic imprinting cross-linked AA/AM/BA graft-esterified cyanoethyl cassava Starch Microspheres. 2.根据权利要求1所述的磁性印迹交联AA/AM/BA接枝酯化氰乙基木薯淀粉微球的应用，其特征在于磁性印迹交联AA/AM/BA接枝酯化氰乙基木薯淀粉微球应用于吸附Cu2+。2. the application of magnetic imprint cross-linking AA/AM/BA graft esterification cyanoethyl tapioca starch microspheres according to claim 1, it is characterized in that magnetic imprint cross-linking AA/AM/BA graft esterification cyanoethyl Tapioca-based microspheres were used to adsorb Cu 2+ .
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