CN107722533A - The preparation method of magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons - Google Patents

The preparation method of magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons Download PDF

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CN107722533A
CN107722533A CN201710924688.6A CN201710924688A CN107722533A CN 107722533 A CN107722533 A CN 107722533A CN 201710924688 A CN201710924688 A CN 201710924688A CN 107722533 A CN107722533 A CN 107722533A
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tapioca
cyanoethyl
hours
distilled water
grafting
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李和平
龚俊
张淑芬
杨莹莹
胡英相
冯璇
张俊
钱敬侠
左凯
杨世军
黄红霞
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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/16—Ether-esters
    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives

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  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a kind of preparation method of magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons.Using tapioca as initiation material, acrylonitrile is etherifying agent, and cyanoethyl tapioca is synthesized through Michael's addition；Again through CS2Lactate synthesis xanthic acid is esterified cyanoethyl tapioca；Continue in the presence of internal crosslinker N, N ' methylene-bisacrylamides, crosslinking AA/AM grafting esterification cyanoethyl tapiocas are obtained through grafting, cross-linking reaction with acrylic acid (AA), acrylamide (AM) mix monomer.Then cyanoethyl tapioca and Fe are esterified to be crosslinked AA/AM grafting3O4For raw material, magnetic starch derivatives microballoon is made by crosslinking in anti-newborn phase solution.Magnetic starch derivatives microballoon prepared by the present invention has the multifunctionality of composite modified starch, has under outside magnetic field condition displacement again and the advantages of quick separation of solid and liquid.

Description

The preparation method of magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons
Technical field
The present invention relates to technical field of fine, particularly a kind of magnetic crosslinking AA/AM grafting esterification cyanoethyl cassavas The preparation method of spherex.
Background technology
Tapioca is a kind of renewable natural resources in Guangxi, and it is changed using active group present in starch Property prepares magnetic starch microcapsule can provide a kind of effective approach for the deep processing of Guangxi cassava starch.Magnetic starch microcapsule is because of bag Magnetic particle is embedded with, can be easily by Magnetic Control, positioning, orientation, movement and measure, therefore magnetic starch microcapsule is in controlled release Agent, pharmaceutical carrier, heavy metal absorbent, cosmetics carrier etc. have quite varied application.It is numerous in magnetic starch microcapsule Excellent properties in, absorption property enjoys people to pay close attention to always, but magnetic starch microcapsule surface made of non-modified starch Functional group is few, activated adoption site deficiency, and absorption or selection adsorption capacity are weaker.By being modified increase function to starch Group is a major issue using the absorption of other technologies raising magnetic starch microcapsule or selection adsorption capacity.
The current research for magnetic starch microcapsule both at home and abroad is with magnetic native starch microballoon and the modification of magnetic list mostly Based on spherex, and the report that magnetic starch microcapsule is prepared using composite modified starch as carrier is relatively fewer.Single modified starch Although compensate for some defects of native starch, still have several drawbacks, and composite modified starch is possessing single modified starch The deficiency of single modified starch is also overcomed while advantage, by being etherified, aoxidizing, amination, esterification, graft copolymerization etc. it is a series of Chemical modification, the active group of starch can be increased, product is obtained higher premium properties.Cyanoethyl starch has preferably glutinous Stability is spent, or even ehter bond is also stable to hydrolysis in high ph-values.The stereochemical structure of starch xanthate it is close and And its configuration is variable, a kind of ion exchange flocculant well can be used as in the industrial production, flocculation for heavy metal and heavy Form sediment helpful.Composite modified starch magnetic microsphere is esterified while with various active functional group by grafting etherificate Have magnetic microsphere can be in the characteristic of displacement under magnetic fields again, this research to starch adsorption performance has particularly significant Meaning.
The present invention is using tapioca as raw material, and acrylonitrile is etherifying agent, and carbon disulfide is esterifying agent, by being etherified, being esterified Two-step reaction has synthesized xanthic acid esterification cyanoethyl tapioca；Then deposited in internal crosslinker N, N '-methylene-bisacrylamide Under, with acrylic acid (AA), acrylamide (AM) for monomer, composite modified starch is obtained through being grafted, being crosslinked；With composite modified shallow lake Powder and Fe3O4For raw material, purpose product magnetic crosslinking AA/AM grafting esterification cyanoethyls are made by crosslinking in anti-newborn phase solution Tapioca microballoon.
The content of the invention
It is an object of the invention to provide a kind of preparation side of magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons Method
Concretely comprise the following steps：
(1) 5~10g tapiocas are placed in 60 DEG C of vacuum drying chambers and dry 24 hours to constant weight, obtain butt para arrowroot Powder.
(2) butt tapioca obtained by 4g steps (1) is taken in four-hole boiling flask, adds 10~15mL distilled water, and by four Mouth flask is placed in heating stirring in 40~50 DEG C of thermostat water bath and is made into the starch emulsion that mass fraction is 20%~30%.
(3) 0.02~0.03g sodium hydroxides are weighed respectively and 0.2~0.4g anhydrous sodium sulfates are dissolved in 5~8mL distilled water In, added under agitation in 15~20 minutes in starch emulsion obtained by step (2), stir-activating 30 minutes, then add 1~ 2mL analyzes pure acrylonitrile, continues reaction 4~6 hours.
(4) step (3) resulting material is washed 2~3 times with the ethanol that 10~15mL mass fractions are 95%, then with 10~ 15mL analyzes pure absolute ethyl alcohol and washed 2~3 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 and dries 12 hours to constant weight, obtain cyanogen Ethyl tapioca.
(6) the cyanoethyl tapioca obtained by 4~5g steps (5) is taken in another four-hole boiling flask, is added 10~15mL and is steamed Distilled water is configured to cyanoethyl tapioca solution.
(7) take the sodium hydroxide solution that 1~1.2mL mass fractions are 10% to add in step (6) solution, stir lower activate 20~30 minutes.
(8) 1~2mL carbon disulfide is rapidly joined in step (7) reaction system, 30~45 DEG C of temperature is controlled, under stirring Carry out esterification 2 hours.
(9) take 0.5~0.7g magnesium sulfate and 9~10mL distilled water to be dissolved in 50mL small beakers, be subsequently poured into step (8) thing Increase the stability of product in material, continue reaction 10 minutes, obtain being esterified cyanoethyl tapioca solution.
(10) 0.15~0.2g ammonium persulfates, 0.3~0.4g sodium hydrogensulfites and 4~6mL distilled water is weighed to burn in 50mL In cup, stirring and dissolving obtains initiator solution at room temperature.
(11) step (9) resulting material is warming up to 45 DEG C, adds 1~2mL steps (10) gained initiator solution, stir Mix 10~20 minutes.
(12) 1~2g acrylic acid, 1~2g acrylamide monomers and 0.04~0.06g crosslinking agents N, N '-methylene are weighed respectively Base bisacrylamide adds 5~10mL distilled water and is well mixed to obtain monomer mixed solution in 50mL small beakers, pours into 100mL perseverances Press standby in dropping funel；Remaining initiator solution in step (10) is poured into again standby in another 100mL constant pressure funnels With.
(13) while monomer mixed solution and initiator solution obtained by step (12) is slowly added dropwise, control time for adding is 3~4 Hour is synchronously added dropwise, and continues reaction 2 hours after addition.
(14) step (13) resulting material is filtered, filter cake analyzes pure nothing with 10~20mL distilled water, 10~20mL successively Water-ethanol and 10~20mL analysis pure acetones wash filter cake 2~3 times respectively；Filter cake is put into glass dish again, is placed in 45 DEG C very Dried 24 hours in empty drying box, AA/AM grafting esterification cyanoethyl tapioca crude products must be crosslinked.
(15) crude product obtained by step (14) is placed in Soxhlet extractor, extracted with 100~150mL analysis pure acetones 24~36 hours；The material after extracting is taken out, is placed in 50 DEG C of vacuum drying chambers and dries 12 hours to constant weight, produce product crosslinking AA/AM grafting esterification cyanoethyl tapiocas.
(16) 160~200mL is analyzed into pure hexamethylene to add in 500mL four-hole boiling flasks, is placed in 60 DEG C of stirred in water bath, adds Enter 0.5~0.6g chemistry pure Tween 60 of pure Span 80 and 0.5~0.6g chemistry, stir emulsified 30 minutes.
(17) crosslinking AA/AM grafting esterification cyanoethyl tapioca obtained by 2~2.5g steps (15) is taken to be placed in the small burnings of 100mL In cup, 20~25mL distilled water is added, is 10~11 with the sodium hydroxide solution regulation pH of 0.5~0.8mL mass fractions 10%, In step (16) system of addition.
(18) 0.4~0.5g ferroso-ferric oxides are taken, 1~1.2mL analysis pure epoxy chloropropanes sequentially add step (17) body In system, continue reaction at 60 DEG C 4~6 hours.
(19) after the completion of reacting, mixed liquor is poured into beaker, the ethanol for adding 40~50mL volume fraction 95% is broken Breast, stood 12 hours.Suction filtration separates to obtain grey black filter cake, analyzes pure nothing with 20~30mL distilled water and 20~30mL successively Water-ethanol alternately washing 3~4 times, then filter cake is put into 60 DEG C of vacuum drying chambers and dried 24 hours, produce magnetic crosslinking AA/AM Grafting esterification cyanoethyl tapioca microballoon.
(20) determination of acid-basetitration etherification starch substitution value is used, concrete operation method is as follows：Take 0.25g cyanoethyls wooden Sweet potato starch is added in conical flask, adds the sodium hydroxide solution of 10mL distilled water and 5mL concentration for 0.5mol/L, mixture concussion Shake up 1 hour, add 2~3 drop phenolphthalein indicators, fully shake up, mixed liquor is in light red (or reddish violet), is with concentration 0.5mol/L normal hydrochloric acid liquid is titrated to untill mixed liquor becomes colorless.The etherificate that cyanoethyl tapioca is calculated as follows takes For degree DS：
In formula：
The etherificate substitution value of DS --- cyanoethyl tapioca；
V1--- add the volume of sodium hydroxide solution, Unit/mL；
V2--- the volume of consumption hydrochloric acid solution, Unit/mL；
C1--- the concentration of sodium hydroxide solution, unit mol/L；
C2--- the concentration of hydrochloric acid solution, unit mol/L；
The quality of m --- etherification starch, unit g；
The mass fraction of w --- cyano group, %.
(21) it is as follows to be crosslinked AA/AM grafting esterification cyanoethyl tapioca test methods of sulphur contents：0.1g is weighed with filter paper Sample, and it is good with filter paper packing.10mL 1.2% H is added in Molotov cocktail2O2Absorbing liquid, logical oxygen (are sufficiently displaced from for 2 minutes Air in flask), ignited filter paper immediately, and it is carefully sent into bottle and burnt, after completely burned, constantly rock flask with Fully absorb.Bottle stopper is opened, boils absorbing liquid 5min, after cooling, the 0.1% methyl red-methylene blue for adding 3~5 drops refers to Show agent, untill suddenly becoming green by aubergine with 0.05mol/L borax standard liquid volumetric soiutions.
The calculation formula of sulfur content in sample：
In formula：
S --- sulfur content in sample, %；
C --- the concentration of borax standard liquid, unit mol/L；
V --- the volume of borax titer used, Unit/mL during titration absorbing liquid；
The quality of W --- sample, unit g；
The relative atomic mass of 32.06-element sulphur.
(22) monomer grafting rate and grafting efficiency in product are determined, specific method and step are as follows：AA/AM will be quantitatively crosslinked Grafting esterification cyanoethyl tapioca crude product sample in apparatus,Soxhlet's with analyzing pure acetone as solvent extraction 24 hours, Remove the graft copolymer purified after homopolymer.The calculation formula of grafting rate and grafting efficiency is as follows：
In formula：
Wg--- the quality of graft esterification copolymer, unit g；
W0--- the quality of former bagasse xylan, unit g；
W1--- the quality of grafted branches, unit g；
W2--- the quality of monomer, unit g.
(23) magnetic crosslinking AA/AM is connect at normal temperatures using the JDM-13 types vibrating specimen magnetometer of Jilin University's production The magnetic property of branch esterification cyanoethyl tapioca microballoon is measured.Method is as follows：The testing sample for weighing up quality is loaded sample Product cup is placed on specimen holder, specific magnetization-magnetic field dependence curve of point-to-point measurement sample (magnetic field is first added to positive maximum, Maximum is reversely added to after falling back on zero, positive maximum is then added to, forms closed curve), obtained comparing saturated magnetization by hysteresis curve figure Intensity.
Clear superiority is possessed by the present invention：
Magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons prepared by the present invention both have composite modified starch The advantages of containing multi-functional group, again with magnetic starch microcapsule the displacement under outside magnetic field condition and quick solid-liquid The advantages of separation.Available for adsorption of metal ions, it is easily separated, secondary pollution will not be caused, repeat utilize the advantages that.
Brief description of the drawings
Fig. 1 schemes for log sweet potato starch IR.
Fig. 2 is that magnetic prepared by the present invention is crosslinked AA/AM grafting esterification cyanoethyl tapioca microballoon IR figures.
Fig. 3 is log sweet potato starch SEM shape appearance figures.
Fig. 4 is that magnetic prepared by the present invention is crosslinked AA/AM grafting esterification cyanoethyl tapioca microballoon SEM shape appearance figures.
Fig. 5 is that magnetic prepared by the present invention is crosslinked AA/AM grafting esterification cyanoethyl tapioca microballoon hysteresis curve figures.
Embodiment
Embodiment：
(1) 6g tapiocas are placed in 60 DEG C of vacuum drying chambers and dry 24 hours to constant weight, obtain butt tapioca.
(2) butt tapioca obtained by 4g steps (1) is taken in 250mL four-hole boiling flasks, adds 12mL distilled water, and by four Mouth flask is placed in heating stirring in 45 DEG C of thermostat water bath and is made into uniform starch emulsion.
(3) 0.03g sodium hydroxides are weighed respectively and 0.2g anhydrous sodium sulfates are dissolved in 5mL distilled water, 15 points under agitation Added in clock in starch emulsion obtained by step (2), stir-activating 30 minutes, then add 2mL and analyze pure acrylonitrile, continue to react 5 hours.
(4) step (3) resulting material is washed 3 times with the ethanol that 15mL mass fractions are 95%, then it is pure with 15mL analyses Absolute ethyl 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 and dries 12 hours to constant weight, obtain cyanogen Ethyl tapioca.
(6) the cyanoethyl tapioca obtained by 4g steps (5) is taken in another four-hole boiling flask, is added 12mL distilled water and is prepared Into cyanoethyl tapioca solution.
(7) take the sodium hydroxide solution that 1.0mL mass fractions are 10% to add in step (6) solution, stir lower activation 30 Minute.
(8) 2mL carbon disulfide is rapidly joined in step (7) reaction system, controls 30 DEG C of temperature, be esterified under stirring Reaction 2 hours.
(9) 0.5g magnesium sulfate, 9.5mL distilled water are taken, is dissolved in 50mL small beakers, is subsequently poured into step (8) material and increases Add the stability of product, continue reaction 10 minutes, obtain being esterified cyanoethyl tapioca solution.
(10) 0.16g ammonium persulfates, 0.34g sodium hydrogensulfites and 4.5mL distilled water are weighed in 50mL beakers, at room temperature Stirring and dissolving obtains initiator solution.
(11) step (9) resulting material is warming up to 45 DEG C, adds 1.5mL steps (10) gained initiator solution, stir Mix 20 minutes.
(12) 1g analyses pure acrylic acid, 1g acrylamide monomers and 0.04g crosslinking agents N, N '-di-2-ethylhexylphosphine oxide third are weighed respectively Acrylamide adds 5mL distilled water and is well mixed to obtain monomer mixed solution, pour into 100mL constant pressure funnels in 50mL small beakers It is interior standby.Remaining initiator solution in step (10) is poured into again standby in another 100mL constant pressure funnels.
(13) while monomer mixed solution and initiator solution obtained by step (12) is slowly added dropwise, control time for adding is small 3 When be synchronously added dropwise, continue after addition reaction 2 hours.
(14) step (13) resulting material is filtered, filter cake successively with 15mL distilled water, 15mL analyze pure absolute ethyl alcohol, 15mL analysis pure acetones wash filter cake 2 times respectively；Filter cake is put into glass dish again, is placed in 45 DEG C of vacuum drying chambers and dries 24 Hour, AA/AM grafting esterification cyanoethyl tapioca crude products must be crosslinked.
(15) crude product obtained by step (14) is placed in Soxhlet extractor, it is small with 150mL analysis pure acetone extractings 24 When；The material after extracting is taken out, is placed in 50 DEG C of vacuum drying chambers and dries 12 hours to constant weight, produce product crosslinking AA/AM and connect Branch esterification cyanoethyl tapioca.
(16) 180mL is analyzed into pure hexamethylene to add in 500mL four-hole boiling flasks, is placed in 60 DEG C of stirred in water bath, added The 0.5g chemistry pure Span 80 and 0.5g pure Tween 60 of chemistry, are stirred emulsified 30 minutes.
(17) crosslinking AA/AM grafting esterification cyanoethyl tapioca obtained by 2g steps (15) is taken to be placed in 100mL small beakers, 20mL distilled water is added, is 10 with the sodium hydroxide solution of 0.5mL mass fractions 10% regulation pH, adds in step (16) system.
(18) 0.4g ferroso-ferric oxides and 1mL is taken to analyze pure epoxy chloropropane and sequentially add in step (17) system, 60 DEG C Under continue reaction 5 hours.
(19) after the completion of reacting, mixed liquor is poured into beaker, adds the ethanol demulsification of 40mL volume fraction 95%, will It stands 12 hours.Suction filtration separates to obtain grey black filter cake, analyzes pure absolute ethyl alcohol with 20mL distilled water and 20mL successively and alternately washes Wash 4 times, then filter cake is put into 60 DEG C of vacuum drying chambers and dried 24 hours, produce magnetic crosslinking AA/AM grafting esterification cyanoethyls Tapioca microballoon.
(20) the etherificate substitution value for measuring product is 0.110, sulfur content 5.76%, grafting rate 70.01%, grafting effect Rate is 89.97%.Between -6000~6000Oe, specific saturation magnetization is its magnetic vibration scope at room temperature 25.10emu/g。
Product is analyzed through IR, in 2251.25cm-1The absworption peak at place is C ≡ N stretching vibration peak, illustrate tapioca with There occurs etherification reaction for acrylonitrile；In 621.00cm-1The absworption peak at place is C-S stretching vibration peak, in 1511.00cm-1Place Weak absorbing peak be C=S stretching vibration peak, showing etherification starch, there occurs esterification with carbon disulfide； 3180.07cm-1The absworption peak at place is-OH stretching vibration peak, in 1706.76cm-1The absworption peak at place is carboxylic carbonyl C=O Stretching vibration peak, in 1569.04cm-1The absworption peak at place is acid amides N-H flexural vibrations peak, 1400.26cm-1There is acid amides C-N stretching vibration peak, illustrate that there occurs graft copolymerization for acrylic acid, acrylamide and modified starch；In 587.25cm-1 For Fe-O stretching vibration absworption peak, illustrate Fe3O4Wrap up successfully.

Claims (1)

  1. A kind of 1. preparation method of magnetic crosslinking AA/AM grafting esterification cyanoethyl tapioca microballoons, it is characterised in that specific step Suddenly it is：
    （1）5 ~ 10g tapiocas are placed in 60 DEG C of vacuum drying chambers and dry 24 hours to constant weight, obtain butt tapioca；
    （2）Take 4g steps（1）Gained butt tapioca adds 10 ~ 15mL distilled water in four-hole boiling flask, and by four-hole boiling flask It is placed in heating stirring in 40 ~ 50 DEG C of thermostat water bath and is made into the starch emulsion that mass fraction is 20% ~ 30%；
    （3）0.02 ~ 0.03g sodium hydroxides are weighed respectively and 0.2 ~ 0.4g anhydrous sodium sulfates are dissolved in 5 ~ 8mL distilled water, are being stirred Step is added in lower 15 ~ 20 minutes（2）In gained starch emulsion, stir-activating 30 minutes, then add 1 ~ 2mL and analyze pure propylene Nitrile, continue reaction 4 ~ 6 hours；
    （4）By step（3）Resulting material is washed 2 ~ 3 times with the ethanol that 10 ~ 15mL mass fractions are 95%, then is analyzed with 10 ~ 15mL Pure absolute ethyl alcohol washs 2 ~ 3 times, filters to obtain filter cake；
    （5）By step（4）Gained filter cake is put into surface plate, is placed in 60 DEG C of baking ovens and is dried 12 hours to constant weight, obtains cyanoethyl Tapioca；
    （6）Take 4 ~ 5g steps（5）The cyanoethyl tapioca of gained adds 10 ~ 15mL distilled water and matched somebody with somebody in another four-hole boiling flask Cyanoethyl tapioca solution is made；
    （7）The sodium hydroxide solution that 1 ~ 1.2mL mass fractions are 10% is taken to add step（6）In solution, lower activation 20 ~ 30 is stirred Minute；
    （8）1 ~ 2mL carbon disulfide is rapidly joined into step（7）In reaction system, 30 ~ 45 DEG C of temperature is controlled, stirs lower progress ester Change reaction 2 hours；
    （9）Take 0.5 ~ 0.7g magnesium sulfate and 9 ~ 10mL distilled water to be dissolved in 50mL small beakers, be subsequently poured into step（8）Increase in material Add the stability of product, continue reaction 10 minutes, obtain being esterified cyanoethyl tapioca solution；
    （10）0.15 ~ 0.2g ammonium persulfates, 0.3 ~ 0.4g sodium hydrogensulfites and 4 ~ 6mL distilled water are weighed in 50mL beakers, room The lower stirring and dissolving of temperature obtains initiator solution；
    (11) by step（9）Resulting material is warming up to 45 DEG C, adds 1 ~ 2mL steps（10）Gained initiator solution, stirring 10 ~ 20 minutes；
    （12）1 ~ 2g acrylic acid, 1 ~ 2g acrylamide monomers and 0.04 ~ 0.06g crosslinking agents are weighed respectivelyN,N´- di-2-ethylhexylphosphine oxide third Acrylamide adds 5 ~ 10mL distilled water and is well mixed to obtain monomer mixed solution in 50mL small beakers, pours into the leakage of 100mL constant pressure additions It is standby in bucket；Again by step（10）In remaining initiator solution pour into it is standby in another 100mL constant pressure funnels；
    （13）Step is slowly added dropwise simultaneously（12）Gained monomer mixed solution and initiator solution, control time for adding was at 3 ~ 4 hours Synchronously it is added dropwise, continues reaction 2 hours after addition；
    （14）By step（13）Resulting material filters, filter cake successively with 10 ~ 20mL distilled water, the pure absolute ethyl alcohol of 10 ~ 20mL analyses, 10 ~ 20mL analysis pure acetones wash filter cake 2 ~ 3 times respectively；Filter cake is put into glass dish again, is placed in 45 DEG C of vacuum drying chambers Dry 24 hours, AA/AM grafting esterification cyanoethyl tapioca crude products must be crosslinked；
    （15）By step（14）The crude product of gained is placed in Soxhlet extractor, with 100 ~ 150mL analysis pure acetones extracting 24 ~ 36 Hour；The material after extracting is taken out, is placed in 50 DEG C of vacuum drying chambers and dries 12 hours to constant weight, produce product crosslinking AA/AM Grafting esterification cyanoethyl tapioca；
    （16）160 ~ 200mL is analyzed into pure hexamethylene to add in 500mL four-hole boiling flasks, is placed in 60 DEG C of stirred in water bath, adds 0.5 ~ the 0.6g chemistry pure Span 80 and 0.5 ~ 0.6g pure Tween 60 of chemistry, are stirred emulsified 30 minutes；
    （17）Take 2 ~ 2.5g steps（15）Gained crosslinking AA/AM grafting esterification cyanoethyl tapiocas are placed in 100mL small beakers, 20 ~ 25mL distilled water is added, is 10 ~ 11 with the sodium hydroxide solution regulation pH of 0.5 ~ 0.8mL mass fractions 10%, adds step Arrive（16）In system；
    （18）0.4 ~ 0.5g ferroso-ferric oxides are taken, 1 ~ 1.2mL analysis pure epoxy chloropropanes sequentially add step（17）In system, 60 Continue reaction at DEG C 4 ~ 6 hours；
    （19）After the completion of reaction, mixed liquor is poured into beaker, the ethanol demulsification of 40 ~ 50mL volume fraction 95% is added, by it Stand 12 hours；Suction filtration separates to obtain grey black filter cake, analyzes pure absolute ethyl alcohol with 20 ~ 30mL distilled water and 20 ~ 30mL successively and hands over For washing 3 ~ 4 times, then filter cake is put into 60 DEG C of vacuum drying chambers and dried 24 hours, produce magnetic crosslinking AA/AM grafting esterifications Cyanoethyl tapioca microballoon.
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CN112774641A (en) * 2021-01-12 2021-05-11 西安理工大学 Preparation method of carboxyl modified magnetic starch-based adsorption material
CN113368832A (en) * 2021-06-25 2021-09-10 吉林大学 Adsorbent material and preparation method and application thereof
CN114130318A (en) * 2021-12-03 2022-03-04 四川大川合颐生物科技有限公司 Large-scale production equipment for microspheres

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN109400810A (en) * 2018-10-21 2019-03-01 桂林理工大学 A kind of synthetic method of complex denaturation xanthic acid esterification-AA/MA/EA grafting-amination tapioca
CN111041014A (en) * 2019-12-31 2020-04-21 浙江工业大学 Magnetic immobilized lipase and application thereof in resolution of 1-methyl-3-amphetamine
CN111041014B (en) * 2019-12-31 2022-03-18 浙江工业大学 Magnetic immobilized lipase and application thereof in resolution of 1-methyl-3-amphetamine
CN112774641A (en) * 2021-01-12 2021-05-11 西安理工大学 Preparation method of carboxyl modified magnetic starch-based adsorption material
CN113368832A (en) * 2021-06-25 2021-09-10 吉林大学 Adsorbent material and preparation method and application thereof
CN113368832B (en) * 2021-06-25 2022-11-18 吉林大学 Adsorbent material and preparation method and application thereof
CN114130318A (en) * 2021-12-03 2022-03-04 四川大川合颐生物科技有限公司 Large-scale production equipment for microspheres
CN114130318B (en) * 2021-12-03 2024-05-28 四川大川合颐生物科技有限公司 Large-scale production equipment for microspheres

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