CN105618002B - modified starch/graphene oxide magnetic composite microsphere and preparation method thereof - Google Patents
modified starch/graphene oxide magnetic composite microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of modified starch/graphene oxide magnetic composite microsphere, the magnetic composite microsphere is made up of following material according to mass parts：30 ~ 60 parts of graphene oxide suspension, it is gelatinized 31 ~ 62 parts of corn starch solution, magnetic Fe3O410.2 ~ 10.4 parts of suspension, 2 ~ 4 parts of acrylamide, 10.3 ~ 10.6 parts of epoxychloropropane solution, 150 ~ 300 parts of castor oil, 80 0.4 ~ 0.8 part of 80 5.6 ~ 11.2 parts of emulsifying agent Span, emulsifying agent Tween；The invention also discloses a kind of preparation method of modified starch/graphene oxide magnetic composite microsphere, and the magnetic microsphere prepared by the present invention is to Cr（III）And Cr（Ⅵ）Clearance can reach more than 98%, while be easily isolated under external magnetic field, can be used repeatedly after desorption.
Description
Technical field
The invention belongs to technical field of absorbent, and in particular to a kind of modified starch/graphene oxide magnetic composite microsphere
And preparation method thereof.
Technical background
Chromium mainly has Cr in nature（VI）And Cr（III）Two kinds of more stable valence states, by surrounding environment such as water
The influence of the factors such as body pH value, organic matter, temperature, Cr VI and trivalent chromium compound can be converted mutually, wherein Cr VI oxygen
The property changed is strong, big to the toxicity of human body, generally more than 100 times of trivalent chromium.The source of chromate waste water is very extensive, plating,
The industries such as process hides, metallurgy, printing and dyeing all using a large amount of bichromates for being used for manufacturing various catalyst and inorganic chromium pigment, are particularly
Chrome tanning agent is widely used in the process for tanning in leather industry, largely contains Cr so as to give off in process of production（IIII）
Waste water, Cr under certain condition（III）Cr can be converted into（VI）, as Cr in water（VI）Content is accumulated over 0.1mg/L
When, will do harm to huamn body.Therefore, Cr（III）And Cr（VI）Content is the big event in water pollution control index,
Must strict processing waste water containing chrome.
Graphene oxide is the derivative of graphene, is a kind of widely used nano material, stannic oxide/graphene nano piece
Layer not only possesses the specific surface area of super large, and containing oxy radicals such as substantial amounts of hydroxyl, carboxyl, epoxy radicals, can be by quiet
Electro ultrafiltration, pi-pi bond etc. and Cr（III）And Cr（VI）Produce interaction and be adsorbed on its surface, so as to reach the mesh of removal
's.Compared with CNT, graphene oxide price is less expensive, while biocompatibility is more preferable；Compared with graphene, stone is aoxidized
Black alkene has good compatibility with many solvents, therefore is widely used in water treatment field.
Starch is one of polysaccharide the abundantest in nature, have it is biodegradable, it is cheap, to the nontoxic pair of environment
The advantages that effect, can be a kind of adsorbent for heavy metal of function admirable with various metals ions binding.Acrylamide is water-soluble
Property is stronger, different molecular weight and the polyacrylamide derivative of charge density can be generated after polymerization, the acyl on its molecular backbone
Amido and double bond have good reactivity.Starch is with acrylamide monomer by starch-grafted made from graft copolymerization
Copolymer is a kind of new functional high molecule material, and it not only remains the high molecular chemical characters of native starch, also has grafting concurrently
The performance of monomer, it can be widely applied to the industries such as environmental protection, petrochemical industry, papermaking and water process.The content of the invention
It is an object of the invention to provide a kind of modified starch/graphene oxide magnetic composite microsphere and preparation method thereof.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：
The embodiment of the present invention provides a kind of modified starch/graphene oxide magnetic composite microsphere, the magnetic composite microsphere by
Following material is made according to mass parts：30 ~ 60 parts of graphene oxide suspension, it is gelatinized 31 ~ 62 parts of corn starch solution, acryloyl
2 ~ 4 parts of amine, magnetic Fe3O410.2 ~ 10.4 parts of suspension, 10.3 ~ 10.6 parts of epoxychloropropane solution, 150 ~ 300 parts of castor oil,
0.4 ~ 0.8 part of 5.6 ~ 11.2 parts of emulsifying agent Span-80, emulsifying agent Tween-80.
In such scheme, the mass fraction of the graphene oxide layer contained by the graphene oxide suspension is 0.1%,
The thickness of stannic oxide/graphene nano lamella is that 3 ~ 10nm, length and width are 30 ~ 80nm.
In such scheme, the gelatinization corn starch solution is by 3 ~ 6 parts of cornstarch and 30 ~ 60 parts of graphene oxides point
Dispersion liquid, 0.1 ~ 0.2 part of ammonium persulfate magnetic agitation 30 minutes at 90 DEG C, and be 30%NaOH solution regulation pH with mass fraction
To 9 gained.
In such scheme, the magnetic Fe3O4Suspension is by 0.2 ~ 0.4g Fe3O4Powder is dispersed in 10ml mass point
Gained in the polyethylene glycol 2000 solution that number is 5%, magnetic Fe used3O4It is to be prepared by chemical coprecipitation, its is straight
Between 20 ~ 30nm, maximum magnetic saturation intensity is 32.5emu/g in footpath.
In such scheme, the epoxychloropropane solution be by 0.3 ~ 0.6 part of epoxychloropropane be dissolved in 10 parts it is anhydrous
Gained in ethanol.
The embodiment of the present invention also provides a kind of preparation method of modified starch/graphene oxide magnetic composite microsphere, by 31 ~
62 parts of gelatinization corn starch solutions and 10.2 ~ 10.4 parts of Fe3O4Ultrasound 30 minutes after suspension is well mixed, then with 2 ~ 4 parts of propylene
Acid amides mixing be used as aqueous phase system, be added dropwise to by 200 ~ 300 parts of castor oil, 5.6 ~ 11.2 parts of Span-80,0.4 ~ 0.8 part
In the oil-based system of Tween-80 compositions, time for adding is 1 hour, continues stirring 1 hour after being added dropwise to complete, then by 10.3 ~
10.6 parts of epoxychloropropane solution are added drop-wise in mixed system, and time for adding is 30 minutes, is added dropwise to complete follow-up continuous insulation reaction 3
Hour, it is demulsified with 30%NaOH solution, mixed system centrifuges, and sediment washs 3 ~ 5 times with acetone, absolute ethyl alcohol respectively, very
Dried 8 hours at empty 60 DEG C, products therefrom is modified starch/graphene oxide magnetic composite microsphere.
Compared with prior art, the present invention has advantages below：
The present invention first by cornstarch and nano graphene oxide it is compound after be grafted again with acrylamide, simultaneously add
Enter Fe3O4Particle assigns its magnetic, and acrylamide graft starch/graphene oxide magnetic is prepared by reversed-phase emulsion cross-linking method
Property complex microsphere.Nontoxic castor oil is used as oil phase dispersion liquid, secondary recovery utilization can be also carried out after the completion of reaction, reacts bar
Part is gentle, green.Make excellent properties of the magnetic microsphere in combination with starch, acrylamide and graphene oxide by oneself, no
Only possess the specific surface area of super large, active group enriches, and green, is easy to degrade, while magnetic Fe3O4The introducing of particle makes
Its easy quick separating after adsorption saturation is reached.Therefore, the homemade acrylamide graft starch/graphene oxide magnetic is answered
Close microballoon heavy metal Cr（III）And Cr（VI）Clearance it is high, application prospect is good.
Embodiment
With reference to embodiment, the present invention is described in detail.
The embodiment of the present invention provides a kind of modified starch/graphene oxide magnetic composite microsphere, the magnetic composite microsphere
It is made up of following material according to mass parts：
30 ~ 60 parts of stannic oxide/graphene nano lamella suspension, it is gelatinized 31 ~ 62 parts of corn starch solution, magnetic Fe3O4Suspend
10.2 ~ 10.4 parts of liquid, 2 ~ 4 parts of acrylamide, 10.3 ~ 10.6 parts of epoxychloropropane solution, 150 ~ 300 parts of castor oil, emulsifying agent
0.4 ~ 0.8 part of 5.6 ~ 11.2 parts of Span-80, emulsifying agent Tween-80.
The stannic oxide/graphene nano lamella suspension is made by the following method：40 ~ 80 parts are added into three-necked flask
Mass fraction is 98% concentrated sulfuric acid, is placed in ice-water bath and stirs, and keeping temperature is less than 5 DEG C, in batches slow in 1 hour
6 ~ 12 parts of potassium permanganate and 3 ~ 6 parts of native graphite powder mixtures are added, continue stirring 3 hours；35 DEG C are warming up to, is reacted 6 hours,
200 ~ 280 parts of deionized waters are added drop-wise in reaction system by solution colour after being changed into purple green, and time for adding is 30 minutes, heating
To 50 DEG C, after reacting 40 minutes, the H that 7 ~ 14 parts of mass fractions are 30% is added2O2It is added drop-wise in reaction system, waits solution to be changed into
Continue reaction 30 minutes after golden yellow, centrifugation, be washed with deionized until without SO2- 4 in solution, add 1 ~ 2 part
Dispersant dimethylformamide, ultrasonic wave obtain stannic oxide/graphene nano lamella suspension in scattered 1.5 hours, control graphite oxide
The mass fraction of alkene is 0.1% or so.
The magnetic Fe3O4Suspension is obtained by the following method：Weigh 0.858 part of FeCl2·4H2O and 2.332 part
FeC13·6H2O, it is added in the three-necked flask for filling 100ml distilled water, regulation water temperature is 50 DEG C, letting nitrogen in and deoxidizing, and stirs 30
Minute makes FeC13·6H2O and FeCl2·4H2O dissolves and is well mixed.Then toward ammoniacal liquor is added dropwise in this solution to solution ph
For 9.2 when terminate, be warming up to 85 DEG C, continue reaction 30 minutes.Products therefrom separates through magnet, then with absolute ethyl alcohol and distilled water
It is in neutral to wash repeatedly to solution, and drying at room temperature 24h obtains magnetic Fe in vacuum drying chamber3O4Powder.By 0.2 ~ 0.4g Fe3O4Powder
Body is dispersed in 10ml 5% polyethylene glycol 2000 solution and obtains magnetic Fe3O4Suspension.
The gelatinization corn starch solution is by 3 ~ 6 parts of cornstarch, 30 ~ 60 parts of graphene oxide suspensions, 0.1 ~ 0.2
Part ammonium persulfate is well mixed, and is transferred in three-necked flask, and the temperature that mixed system is warming up under the conditions of magnetic agitation is 90
DEG C, insulation gelatinization 30min, and be 9 gained with 30%NaOH solution regulation pH.
The epoxychloropropane ethanol solution is that the epoxychloropropane of 0.3 ~ 0.6 mass parts is dissolved in into 10 parts of absolute ethyl alcohols
Middle gained.
The present invention also provides a kind of preparation method of modified starch/graphene oxide magnetic composite microsphere, and this method is：Will
31 ~ 62 parts of gelatinization corn starch solutions and 10.2 ~ 10.4 parts of magnetic Fes3O4Ultrasound 30 minutes after suspension is well mixed, then again
It is mixed evenly with 2 ~ 4 parts of acrylamides；Using above-mentioned mixed liquor as aqueous phase, be added drop-wise to by 200 ~ 300 parts of castor oil, 5.6 ~
In the oil phase mixed system of 11.2 parts of Span-80 and 0.4 ~ 0.8 part of Tween-80 compositions, time for adding is 1 hour, is dripped
Continue stirring 1 hour after；10.3 ~ 10.6 parts of epoxychloropropane solution are added drop-wise in mixed system, time for adding is 30 points
Clock, is added dropwise to complete follow-up continuous insulation reaction 3 hours, is demulsified with 30%NaOH solution, and mixed system centrifuges, sediment difference
Washed 3 ~ 5 times, dried 8 hours at 60 DEG C of vacuum, products therefrom is acrylamide graft starch/oxygen with acetone, absolute ethyl alcohol
Graphite alkene magnetic composite microsphere.
Embodiment one：
Step 1：The preparation of graphene oxide dispersion
The concentrated sulfuric acid that 40 parts of mass fractions are 98% is added into three-necked flask, is placed in ice-water bath and stirs, keeping temperature
For less than 5 DEG C, it was slowly added to 6 parts of potassium permanganate and 3 mass parts native graphite powder mixtures in batches in 1 hour, continues stirring 3
Hour；35 DEG C are warming up to, is reacted 6 hours, after solution colour is changed into purple green, 100 parts of deionized waters are added drop-wise to reaction system
In, time for adding is 30 minutes；50 DEG C are warming up to, after reacting 40 minutes, by the H that 7 parts of mass fractions are 30%2O2It is added drop-wise to reaction
In system, wait solution to continue reaction 30 minutes after being changed into golden yellow, centrifugation, be washed with deionized up to nothing in solution
SO2- 4, adds 1.0 parts of dispersant dimethylformamides, and ultrasonic wave obtains stannic oxide/graphene nano lamella in scattered 1.5 hours
Suspension, the mass fraction of graphene oxide is controlled 0.1% or so, it is standby.
Step 2：The preparation of gelatinization of starch solution：
3 parts of cornstarch, 30 parts of graphene oxide suspensions, 0.1 part of ammonium persulfate are well mixed, are transferred to three mouthfuls of burnings
In bottle, the temperature that mixed system is warming up under the conditions of magnetic agitation is 90 DEG C, insulation gelatinization 30min, and with 30%NaOH solution
It is 9 to adjust pH, standby.
Step 3：Magnetic Fe3O4The preparation of dispersion liquid：
Weigh 0.858 part of FeCl2·4H2O and 2.332 part of FeC13·6H2O, it is added to fill 100ml distilled water three mouthfuls
In flask, regulation water temperature is 50 DEG C, letting nitrogen in and deoxidizing, and stirring makes FeC1 in 30 minutes3·6H2O and FeCl2·4H2O dissolves and mixed
Close uniform.Terminated when being then 9.2 toward dropwise addition ammoniacal liquor in this solution to solution ph, be warming up to 85 DEG C, continue reaction 30 minutes.
Products therefrom separates through magnet, then is washed repeatedly to solution in neutral, room temperature in vacuum drying chamber with absolute ethyl alcohol and distilled water
Dry 24h and obtain magnetic Fe3O4Powder.By 0.2g Fe3O4Powder is dispersed in 10ml 5% polyethylene glycol 2000 solution and obtains magnetic
Property Fe3O4Suspension, it is standby.
Step 4：The preparation of epoxychloropropane solution：
0.3 part of epoxychloropropane is dissolved in 10 parts of absolute ethyl alcohols, it is standby after being stirred until homogeneous.
Step 5：The preparation of oil phase：
It is placed in after 200 parts of castor oil are well mixed with 5.6 parts of Span-80,0.4 part of Tween-80 in three-necked flask, in
Stirred 30 minutes under 50 DEG C of water-baths, it is standby.
Step 6：Acrylamide graft starch/graphene oxide magnetic composite microsphere and preparation method thereof：
Will gelatinization corn starch solution and magnetic Fe3O4Ultrasound 30 minutes after suspension is well mixed, then again with 2 part third
Acrylamide is mixed evenly；Using above-mentioned mixed liquor as aqueous phase, it is added drop-wise in oil phase mixed system, time for adding is 1 hour,
Continue stirring 1 hour after being added dropwise to complete；10.3 parts of epoxychloropropane solution are added drop-wise in mixed system, time for adding is 30 points
Clock, is added dropwise to complete follow-up continuous insulation reaction 3 hours, is demulsified with 30%NaOH solution, and mixed system centrifuges, sediment difference
Washed 3 ~ 5 times, dried 8 hours at 60 DEG C of vacuum, products therefrom is acrylamide graft starch/oxygen with acetone, absolute ethyl alcohol
Graphite alkene magnetic composite microsphere.
Embodiment two：
Step 1：The preparation of graphene oxide dispersion
The concentrated sulfuric acid that 80 parts of mass fractions are 98% is added into three-necked flask, is placed in ice-water bath and stirs, keeping temperature
For less than 5 DEG C, 12 parts of potassium permanganate and 6 parts of native graphite powder mixtures were slowly added in batches in 1 hour, it is small to continue stirring 3
When；35 DEG C are warming up to, is reacted 6 hours, after solution colour is changed into purple green, 280 parts of deionized waters are added drop-wise in reaction system,
Time for adding is 30 minutes, is warming up to 50 DEG C, after reacting 40 minutes, by the H that 14 parts of mass fractions are 30%2O2It is added drop-wise to reactant
In system, wait solution to continue reaction 30 minutes after being changed into golden yellow, centrifugation, be washed with deionized until without SO2- in solution
4,2.0 parts of dispersant dimethylformamides are added, ultrasonic wave obtains the suspension of stannic oxide/graphene nano lamella for scattered 1.5 hours
Liquid, the mass fraction of graphene oxide is controlled 0.1% or so, it is standby.
Step 2：The preparation of gelatinization of starch solution：
6 parts of cornstarch, 60 parts of graphene oxide suspensions, 0.2 part of ammonium persulfate are well mixed, are transferred to three mouthfuls of burnings
In bottle, the temperature that mixed system is warming up under the conditions of magnetic agitation is 90 DEG C, insulation gelatinization 30min, and with 30%NaOH solution
It is 9 to adjust pH, standby.
Step 3：Magnetic Fe3O4The preparation of dispersion liquid：
Weigh 0.858 part of FeCl2·4H2O and 2.332 part of FeC13·6H2O, it is added to fill 100ml distilled water three mouthfuls
In flask, regulation water temperature is 50 DEG C, letting nitrogen in and deoxidizing, and stirring makes FeC1 in 30 minutes3·6H2O and FeCl2·4H2O dissolves and mixed
Close uniform.Terminated when being then 9.2 toward dropwise addition ammoniacal liquor in this solution to solution ph, be warming up to 85 DEG C, continue reaction 30 minutes.
Products therefrom separates through magnet, then is washed repeatedly to solution in neutral, room temperature in vacuum drying chamber with absolute ethyl alcohol and distilled water
Dry 24h and obtain magnetic Fe3O4Powder.By 0.4g Fe3O4Powder is dispersed in 10ml 5% polyethylene glycol 2000 solution and obtains magnetic
Property Fe3O4Suspension, it is standby.
Step 4：The preparation of epoxychloropropane solution：
0.6 part of epoxychloropropane is dissolved in 10 parts of absolute ethyl alcohols, it is standby after being stirred until homogeneous.
Step 5：The preparation of oil phase：
It is placed in after 300 parts of castor oil are well mixed with 11.2 parts of Span-80,0.8 part of Tween-80 in three-necked flask, in
Stirred 30 minutes under 50 DEG C of water-baths, it is standby.
Step 6：Acrylamide graft starch/graphene oxide magnetic composite microsphere：
Will gelatinization corn starch solution and Fe3O4Ultrasound 30 minutes after suspension is well mixed, then again with 4 parts of acryloyls
Amine is mixed evenly；Using above-mentioned mixed liquor as aqueous phase, it is added drop-wise in oil phase mixed system, time for adding is 1 hour, is added dropwise
After the completion of continue stirring 1 hour；10.6 parts of epoxychloropropane solution are added drop-wise in mixed system, time for adding is 30 minutes,
It is added dropwise to complete follow-up continuous insulation reaction 3 hours, is demulsified with 30%NaOH solution, mixed system centrifuges, and sediment is respectively with third
Ketone, absolute ethyl alcohol wash 3 ~ 5 times, are dried 8 hours at 60 DEG C of vacuum, products therefrom is acrylamide graft starch/oxidation stone
Black alkene magnetic composite microsphere.
Claims (6)
- A kind of 1. preparation method of modified starch/graphene oxide magnetic composite microsphere, it is characterised in that：By 31 ~ 62 parts of gelatinizations Corn starch solution and 10.2 ~ 10.4 parts of Fe3O4Ultrasound 30 minutes after suspension is well mixed, then mixed with 2 ~ 4 parts of acrylamides As aqueous phase system, it is added dropwise to by 200 ~ 300 parts of castor oil, 5.6 ~ 11.2 parts of Span-80,0.4 ~ 0.8 part of Tween-80 In the oil-based system of composition, time for adding is 1 hour, continues stirring 1 hour after being added dropwise to complete, then by 10.3 ~ 10.6 parts of epoxies Chloropropane solution is added drop-wise in mixed system, and time for adding is 30 minutes, follow-up continuous insulation reaction is added dropwise to complete 3 hours, with 30% NaOH solution is demulsified, and mixed system centrifuges, and sediment is washed 3 ~ 5 times with acetone, absolute ethyl alcohol respectively, is done at 60 DEG C of vacuum Dry 8 hours, products therefrom was modified starch/graphene oxide magnetic composite microsphere；The gelatinization corn starch solution be by 3 ~ 6 parts of cornstarch and 30 ~ 60 parts of graphene oxide dispersions, 0.1 ~ 0.2 part Ammonium persulfate magnetic agitation 30 minutes at 90 DEG C, and obtained by mass fraction is 30%NaOH solution regulation pH to 9.
- 2. changing obtained by the preparation method of modified starch according to claim 1/graphene oxide magnetic composite microsphere Property starch/graphene oxide magnetic composite microsphere, it is characterised in that the magnetic composite microsphere is by following material according to mass parts system Into：It is gelatinized 31 ~ 62 parts of corn starch solution, 2 ~ 4 parts of acrylamide, magnetic Fe3O410.2 ~ 10.4 parts of suspension, epoxy chloropropionate 10.3 ~ 10.6 parts of alkane solution, 200 ~ 300 parts of castor oil, 5.6 ~ 11.2 parts of emulsifying agent Span-80, emulsifying agent Tween-80 0.4 ~ 0.8 part.
- 3. modified starch according to claim 2/graphene oxide magnetic composite microsphere, it is characterised in that：The oxidation The mass fraction of graphene oxide layer contained by graphene suspension is 0.1%, the thickness of stannic oxide/graphene nano lamella for 3 ~ 10nm, length and width are 30 ~ 80nm.
- 4. modified starch according to claim 2/graphene oxide magnetic composite microsphere, it is characterised in that：The gelatinization Corn starch solution is 90 by 3 ~ 6 parts of cornstarch and 30 ~ 60 parts of graphene oxide dispersions, 0.1 ~ 0.2 part of ammonium persulfate Magnetic agitation 30 minutes at DEG C, and obtained by mass fraction is 30%NaOH solution regulation pH to 9.
- 5. modified starch according to claim 2/graphene oxide magnetic composite microsphere, it is characterised in that：The magnetic Fe3O4Suspension is by 0.2 ~ 0.4g Fe3O4Powder is dispersed in 10ml mass fractions as institute in 5% polyethylene glycol 2000 solution , magnetic Fe used3O4It is to be prepared by chemical coprecipitation, for its diameter between 20 ~ 30nm, maximum magnetic saturation is strong Spend for 32.5emu/g.
- 6. modified starch according to claim 2/graphene oxide magnetic composite microsphere, it is characterised in that：The epoxy Chloropropane solution is that 0.3 ~ 0.6 part of epoxychloropropane is dissolved in into gained in 10 parts of absolute ethyl alcohols.
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