CN105732901B - A kind of manioc waste magnetic microsphere and preparation method thereof - Google Patents

A kind of manioc waste magnetic microsphere and preparation method thereof Download PDF

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CN105732901B
CN105732901B CN201610253638.5A CN201610253638A CN105732901B CN 105732901 B CN105732901 B CN 105732901B CN 201610253638 A CN201610253638 A CN 201610253638A CN 105732901 B CN105732901 B CN 105732901B
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manioc waste
magnetic microsphere
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CN105732901A (en
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谢新玲
熊海武
张友全
童张法
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Guangxi University
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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
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • 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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  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Polymerisation Methods In General (AREA)
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Abstract

The invention discloses a kind of manioc waste magnetic microsphere and preparation method thereof, belong to the technical field of magnetic microsphere.The present invention is raw material using solid waste manioc waste, pre-processed using means such as mechanical activations, using atoleine as oil phase, acrylic acid, three kinds of monomers of acrylamide and methyl methacrylate and crosslinking agent N, N ' methylene-bisacrylamides water solution mixture is aqueous phase, and using ammonium persulfate and sodium sulfite as composite initiator, manioc waste magnetic microsphere is prepared for using reversed-phase emulsion cross-linking method.This method is simple to operate, and technique is controllable, and energy consumption is low and oil phase is recyclable.The microballoon balling-up prepared and good dispersion, size uniformity, specific surface area are big.

Description

A kind of manioc waste magnetic microsphere and preparation method thereof
Technical field
The invention belongs to modified starch/cellulose technology field, and in particular to manioc waste magnetic microsphere and preparation method thereof.
Background technology
It is increasingly in short supply with the non-renewable fossil resources such as coal, oil, natural gas, to the development and exploration of new energy Countries in the world are caused widely to be paid close attention to, biomass energy has the advantages that wide material sources, renewable, low stain, has become people The focus that class is studied at present.
Cassava is the important agricultural resource in tropical and subtropical region, belongs to a part for biomass resource.Chinese Cassava Gross annual output amount up to more than 6,000,000 tons, Guangxi is one of China cassava main producing region, and cassava cultivated area and yield account for the whole nation More than 1/ 3.Cassava is mainly for the production of starch, and manioc waste is remaining residue after cassava production starch, and China is every at present Year there are about ten tens of thousands of tons of manioc waste, finds that Tapioca chips slag contains the compositions such as abundant starch and cellulose after measured, has one Fixed development and application potential quality.Exploitation currently for manioc waste is mainly used in mixture feed and biofermentation production alcohol, but disappears Consumption is limited, and most of manioc waste goes out of use, and not only causes the wasting of resources, and seriously pollute environment.
Magnetic macromolecular microsphere is a kind of magnetic responsiveness particulate and the compound material of macromolecule, and it both has magnetic responsiveness thing Matter externally-applied magnetic field control under can fast enriching, separation either fixed point displacement the characteristics of, get both high polymer material table again Face has carboxyl (- COOH), hydroxyl (- OH), amino (- NH2), the characteristic of the functional groups such as sulfydryl (- SH).As a kind of new Type functional material, magnetic macromolecular microsphere have wide in fields such as fine chemistry industry, medical science, bio-separation, environmental treatment, cytology Wealthy prospect, and prepare with meeting different requirements and microballoon with monodispersity and strong magnetic responsiveness becomes the field Focus and difficult point.
Magnetic macromolecular microsphere is prepared both at home and abroad mostly using chitosan as raw material at present, and adds system using chitosan The cost of standby magnetic microsphere；The tapioca magnetic microsphere researched and developed both at home and abroad at present, easy adhesion, dispersiveness are undesirable；It is and fine It is generally bigger than normal to tie up biscuit porcelain microspherulite diameter, limits the application development of microballoon.Contain substantial amounts of cellulose and starch in manioc waste, Compared with chitosan, cellulose and starch also natural polymer, there is degradable and good biocompatibility, can connect Branch monomer, and contain substantial amounts of hydroxyl, storage capacity is big, is the ideal material for preparing magnetic macromolecular microsphere.Therefore, solid is utilized Discarded object manioc waste is that raw material can reduce cost to prepare magnetic microsphere, makes full use of solid waste, reduces to environment Pollution.The relevant report on manioc waste magnetic microsphere composite is not seen also at present.
The content of the invention
The present situation polluted the present invention be directed to manioc waste comprehensive utilization deficiency and after discarding to environment, and existing magnetic Property spherex, dispersiveness is undesirable, the defects of magnetic cellulose microsphere particle diameter is bigger than normal, using manioc waste as raw material, there is provided a kind of Manioc waste magnetic microsphere and preparation method thereof, easy to operate, structure-controllable, the magnetic microsphere of preparation is well dispersed, granularity it is small and Uniformly, magnetic responsiveness is strong, and balling-up is good.
Technical scheme is as follows：
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Pretreated manioc waste and NaOH are added to the water stirring, added after being cooled down under ice-water bath single Body methyl methacrylate, continue to be stirred 20 ~ 40 minutes, then it is 1 that manioc waste and the mass ratio of acrylic acid, which is added dropwise,: 0.625 ~ 35 monomeric acrylic；Monomeric acrylamide, crosslinking agent and Fe are continuously added after cooling3O4Particle；Manioc waste and NaOH Mass ratio be 1: 1~9（NaOH dosages are adjusted according to acrylic acid degree of neutralization, control NaOH and acrylic acid mole is less than 1）； The addition of methyl methacrylate is 1 with manioc waste mass ratio: 8~27；The addition of the acrylamide and acrylic acid Addition mass ratio is 7: 1~50；
（2）Prepare oil phase：According to emulsifying agent and atoleine mass ratio it is 1 by emulsifying agent:8 ~ 10 are added to atoleine Oil phase is made；
（3）The maintaining nitrogen purge into oil phase, 45 ~ 55 DEG C of heating water baths, stirred by the rpm of rotating speed 300 ~ 600, aqueous phase is dripped It is added in oil phase, initiator is added after stirring and emulsifying certain time, reacts 3 ~ 12h.
Initiator in the present invention is ammonium persulfate and the compound system of sodium sulfite, and the addition of ammonium persulfate is monomer The mol ratio of the 0.5% ~ 2% of gross mass, ammonium persulfate and sodium sulfite is 1:1；
（4）React product Magnetic Isolation after terminating, then alternately washed with absolute ethyl alcohol and acetone, then be dried in vacuo, Both manioc waste magnetic microsphere had been can obtain.
Step of the present invention（1）The dosage of middle crosslinking agent is three kinds of acrylic acid, acrylamide and methyl methacrylate monomers The 0.1% ~ 8% of gross mass；The Fe3O4The mass ratio of particle and manioc waste is 4: 1~16.
It is preferred as technical scheme, crosslinking agent N, N '-methylene-bisacrylamide.
Step of the present invention（1）The pretreatment of middle manioc waste is：After raw material manioc waste is pulverized and sieved, handled through mechanical ball mill 0.5-4 h, add mass fraction be 1% ~ 5% NaOH solution in, the h of boiling 3 ~ 12 at 70 ~ 100 DEG C, filtering, take filter residue in Crushed after being dried at 40 ~ 90 DEG C, pretreated manioc waste was both obtained.Wherein raw material manioc waste is with NaOH solution mass ratio 1: 10~40。
Raw material manioc waste is that industrial tapioca factory extracts residue or storage dry slag of the starch after through mechanical dehydration.
Step of the present invention（1）Middle Fe3O4The preparation method of particle is：By FeCl3And FeCl2In molar ratio 1.75 ~ 2: 1 It is added to the water, controls Fe concentration to be maintained at 0.25 ~ 1mol/L, the heating water bath at 70 ~ 90 DEG C, keeps 200 ~ 500 rpm Rotating speed stirs, and adding the ammoniacal liquor that mass fraction is 25% makes solution ph be washed to neutrality after curing 2 ~ 4 h, finally to 9 ~ 10 It is dried in vacuo at 40 ~ 70 DEG C and both can obtain Fe3O4Particle.
As the preferred of technical scheme, mixture that the emulsifying agent in the present invention is OP-4 and SPAN80, mixing quality ratio For 1: 1.75~6.Span80, Chinese Span-80；Sorbitol anhydride oleate；S-80 emulsifying agents, C24H44O6；OP-4 into It is OPEO to divide；It is commercially available to obtain.
As the preferred of technical scheme, the step（3）Aqueous phase is added in oil phase, aqueous phase addition and atoleine Volume ratio is 1: 5~15.
As the preferred of technical scheme, the step（4）Absolute ethyl alcohol and acetone alternately washing 3 ~ 5 times, at 30 ~ 80 DEG C Vacuum drying, both obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 180~300 nm, polydispersity index（PDI）For 0.14 ~ 0.25, the saturation magnetization intensity of microballoon is 10 ~ 21 emu/g.
Except, as comonomer, being also added into methyl-prop using acrylic acid and acrylamide hydrophilic monomer in the present invention E pioic acid methyl ester hydrophobic monomer, the purpose is to reduce microballoon system viscosity, make microballoon adhesion, the micro- of good dispersion can be obtained Ball.
The advantages of present invention combines magnetic material and natural macromolecular material, using solid waste manioc waste as raw material, adopts Manioc waste magnetic microsphere new material is prepared with reversed-phase emulsion cross-linking method, it can effectively be enriched with external magnetic field, separates, Recycle, have broad application prospects in fields such as sewage disposal, cell separation, medical science, environmental monitorings, not only save Cost, environmental pollution is also reduced, be a kind of biochemical industry new product with essential industry value and economic value.
The present invention is pre-processed using means such as mechanical activations to solid waste manioc waste first, using in manioc waste Starch and cellulose be macromolecular scaffold, it is single as copolymerization using acrylic acid/acrylamide/methyl methacrylate compound monomer Body, utilize the compound parcel Fe of reversed-phase emulsion crosslinking technological3O4Magnetic particle, manioc waste and compound monomer are mutual under certain condition Effect, form manioc waste magnetic composite.By adjusting the proportioning of three kinds of different monomers, that realizes micro-sphere structure and granularity can Control synthesis.Microballoon can compound parcel high mixture ratio Fe3O4Magnetic particle, so as to have strong magnetic responsiveness.Microballoon in reversed-phase emulsion into Type, OP-4 and SPAN80 emulsifying agents, which are used cooperatively, make it that emulsion is uniform and stable, so that microsphere particle size is small and uniform, balling-up It is good.Hydrophobic monomer methyl methacrylate is distributed mainly in emulsion at oil-water interfaces, that is, microsphere surface, and class makes micro- Ball surface viscosity reduces, and reduces the microballoon adhesive of current generally existing, improves the dispersiveness of microballoon.
Compared with the prior art, the beneficial effects of the invention are as follows：
1st, the present invention is raw material using solid waste manioc waste, prepares manioc waste magnetic microsphere, not only turns waste into wealth, opens Its new application has been sent out, and has improved its value and economic value.
2nd, the present invention with the addition of hydrophobic methacrylic acid on the basis of acrylic acid, acrylamide hydrophilic monomer Methylmethacrylate monomer, by the addition of the adjustment control monomer, it can reach and reduce microballoon viscosity, the effect of dispersion microsphere.Add Measure it is very few, do not reach reduce viscosity, dispersion microsphere effect, addition is excessive, and the functional group ratio of microsphere surface diminishes, shadow Ring the performance of microballoon.
3rd, manioc waste passes through the pretreating schemes such as mechanical activation, simple to operate, improves manioc waste reactivity；By anti- Phase emulsion crosslinking technological prepares globulate and good dispersion, and surface is smooth, size uniformity, the big feature magnetic of specific surface area Microballoon.
4th, using two kinds of hydrophilic acrylic acid and acrylamide monomer and hydrophobic methyl methacrylate in the present invention Three kinds of monomers of ester, which coordinate, carries out cross-linking reaction, makes the spherical in shape good of microballoon, is uniformly dispersed, adhesion, this method is simple to operate, technique Controllable, energy consumption is low and oil phase is recyclable.There is certain viscosity after polymerizable acrylic monomer, be advantageous to microballoon shaping, and can be micro- Ball offer-COOH；Monomeric acrylamide can provide-NH for microballoon2, and-the COOH provided with acrylic acid coexists according to a certain ratio When have synergy, improve microballoon performance；Methyl methacrylate can reduce microsphere surface viscosity, make microballoon tool good Dispersiveness.
Specific embodiment
The detailed implementation process and concrete operation step of the present invention is given below, one of ordinary skill in the art can be made More fully understand the present invention, but do not limit the invention in any way.
Embodiment 1
The pretreatment of manioc waste：The raw material manioc waste after 50 g are crushed is weighed, 2 h is handled through mechanical ball mill, adds 1 L matter Measure in the NaOH solution that fraction is 2%, the h of water-bath boiling 3 at 90 DEG C, filter residue crushed after being dried at 50 DEG C is taken after filtering, both Obtain pretreated manioc waste.
Fe3O4The preparation of particle：Measure the FeCl that concentration is 0.5 mol/L3The mL of solution 500 and concentration are 0.5 mol/L FeCl2The mL of solution 285.7 mixing keeps 300 rpm rotating speed mechanical agitation, adds 25 wt% after 80 DEG C of heating water baths Ammoniacal liquor make solution ph be 9.5, cure 2 h after be washed to neutrality, finally 50 DEG C vacuum drying, both Fe3O4Particle.
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Accurately weigh 0.817 g NaOH to be dissolved in 5 mL water, add the pretreated wood of 0.4 g Potato slag, the magnetic agitation in ice-water bath, the methyl methacrylate aqueous solution that 3 mL mass fractions are 1% is added after cooling, is stirred 3 mL acrylic acid are added dropwise after mixing 0.5 h, are further continued for adding 1g acrylamides and 0.018 g N, N '-methylene bisacrylamide acyl Amine, after being sufficiently stirred, depart from magnetic agitation, add 0.4 g Fe3O4Particle is simultaneously well mixed.
（2）Prepare oil phase：Weigh 2.63 g OP-4 and 12.37 g SPAN80 to add in 150 mL atoleines, stirring Uniformly, oil phase is made；
（3）Oil phase is moved into three-necked flask, 50 DEG C of heating water baths, maintaining nitrogen purge, stirred by the rpm of rotating speed 450, will Aqueous phase is added dropwise in oil phase, after stirring 0.5 h, is added 1.5 mL initiator solutions, is reacted 3 h.
Initiator solution is prepared in advance：Accurately weigh 3.65 g ammonium persulfates and 2.01 g sodium sulfites are dissolved in 20 mL In water, constant volume in 100 mL volumetric flasks is then moved into.
（4）Reaction separates from emulsion product with magnetic force after terminating, then with absolute ethyl alcohol and acetone alternately washing 3 It is secondary, it is put into vacuum drying chamber at 50 DEG C and dries afterwards, had both can obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 198 nm, polydispersity index（PDI）For 0.18, saturation magnetic Change intensity is 13.2 emu/g.
Embodiment 2
The pretreatment of manioc waste：The former manioc waste after 100 g are crushed is weighed, 4 h is handled through mechanical ball mill, adds 1L mass Fraction is in 5% NaOH solution, the h of water-bath boiling 12 at 70 DEG C, filter residue crushed after being dried at 90 DEG C is taken after filtering, both Pretreated manioc waste.
Fe3O4The preparation of particle：Measure the FeCl that concentration is 0.25 mol/L3Solution 500mL and concentration are 0.25 mol/L FeCl2The mL of solution 285.7 mixing keeps 400 rpm rotating speed mechanical agitation, adds 25 wt% after 90 DEG C of heating water baths Ammoniacal liquor makes solution ph be 10, and neutrality is washed to after curing 4 h, finally in 70 DEG C of vacuum drying, both obtains Fe3O4Particle.
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Accurately weigh 0.817 g NaOH to be dissolved in 5 mL water, add the pretreated wood of 0.4 g Potato slag, the magnetic agitation in ice-water bath, the methyl methacrylate aqueous solution that 2mL mass fractions are 1% is added after cooling, is stirred 2 mL acrylic acid are added dropwise after mixing 0.5 h, are further continued for adding 2g acrylamides and 0.018 g N, N '-methylene bisacrylamide acyl Amine, after being sufficiently stirred, depart from magnetic agitation, add 0.8 g Fe3O4Particle is simultaneously well mixed.
（2）Prepare oil phase：Weigh 5.45 g OP-4 and 9.55 g SPAN80 to add in 150 mL atoleines, stirring is equal It is even, oil phase is made；
（3）Oil phase is moved into three-necked flask, 50 DEG C of heating water baths, maintaining nitrogen purge, stirred by the rpm of rotating speed 300, will Aqueous phase is added dropwise in oil phase, after stirring 0.5 h, is added 1.2 mL initiator solutions, is reacted 6 h.
Initiator solution is prepared in advance：Accurately weigh 3.65 g ammonium persulfates and 2.01 g sodium sulfites are dissolved in 20 mL In water, constant volume in 100 mL volumetric flasks is then moved into.
（4）Reaction separates from emulsion product with magnetic force after terminating, then with absolute ethyl alcohol and acetone alternately washing 4 It is secondary, it is put into vacuum drying chamber at 30 DEG C and dries afterwards, had both can obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 208 nm, and polydispersity index (PDI) is 0.22, saturation magnetic Change intensity is 21 emu/g.
Embodiment 3
The pretreatment of manioc waste：The former manioc waste after 25 g are crushed is weighed, 0.5 h is handled through mechanical ball mill, adds 1L matter Measure in the NaOH solution that fraction is 1%, the h of water-bath boiling 8 at 100 DEG C, filter residue crushed after being dried at 40 DEG C is taken after filtering, both Obtain pretreated manioc waste.
Fe3O4The preparation of particle：Measure the FeCl that concentration is 1 mol/L3The mL of solution 500 and concentration are 1 mol/L's FeCl2The mL of solution 285.7 mixing keeps 500 rpm rotating speed mechanical agitation, adds 25 wt% ammonia after 80 DEG C of heating water baths Water to solution PH is 9, and neutrality is washed to after curing 3 h, finally in 40 DEG C of vacuum drying, both obtains Fe3O4Particle.
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Accurately weigh 0.525 g NaOH to be dissolved in 5 mL water, add the pretreated wood of 0.4 g Potato slag, the magnetic agitation in ice-water bath, the methyl methacrylate aqueous solution that 1 mL mass fractions are 1% is added after cooling, is stirred 1 mL acrylic acid is added dropwise after mixing 0.5 h, is further continued for adding 3 g acrylamides and 0.32 g N, N '-methylene bisacrylamide acyl Amine, after being sufficiently stirred, depart from magnetic agitation, add 0.6 g Fe3O4Particle is simultaneously well mixed.
（2）Prepare oil phase：Weigh 2.14 g OP-4 and 12.86 g SPAN80 to add in 150 mL atoleines, stirring Uniformly, oil phase is made；
（3）Oil phase is moved into three-necked flask, 55 DEG C of heating water baths, maintaining nitrogen purge, stirred by the rpm of rotating speed 450, will Aqueous phase is added dropwise in oil phase, is added 0.55 mL initiator solutions after stirring 0.5 h, is reacted 12 h.
Initiator solution is prepared in advance：Accurately weigh 3.65 g ammonium persulfates and 2.01 g sodium sulfites are dissolved in 20 mL In water, constant volume in 100 mL volumetric flasks is then moved into.
（4）Reaction separates from emulsion product with magnetic force after terminating, then with absolute ethyl alcohol and acetone alternately washing 5 It is secondary, it is put into vacuum drying chamber at 80 DEG C and dries afterwards, had both can obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 182 nm, polydispersity index（PDI）For 0.25, saturation magnetic Change intensity is 16 emu/g.
Embodiment 4
The pretreatment of manioc waste：The former manioc waste after 50 g are crushed is weighed, 1 h is handled through mechanical ball mill, adds 1 L mass Fraction is in 2% NaOH solution, the h of water-bath boiling 5 at 80 DEG C, filter residue crushed after being dried at 60 DEG C is taken after filtering, both Pretreated manioc waste.
Fe3O4The preparation of particle：Measure the FeCl that concentration is 0.5 mol/L3The mL of solution 500 and concentration are 0.5 mol/L FeCl2The mL of solution 285.7 mixing keeps 300 rpm rotating speed mechanical agitation, adds 25 wt% after 70 DEG C of heating water baths Ammoniacal liquor to pH value of solution is 9.5, and neutrality is washed to after curing 2.5 h, finally in 40 DEG C of vacuum drying, both obtains Fe3O4Particle.
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Accurately weigh 2.2872 g NaOH to be dissolved in 9 mL water, add the pretreated cassavas of 1 g Slag, the magnetic agitation in ice-water bath, the methyl methacrylate aqueous solution that 3 mL mass fractions are 1%, stirring is added after cooling 9 mL acrylic acid are added dropwise after 0.5 h, are further continued for adding 1.28 g acrylamides and 0.825 g N, N '-methylene bisacrylamide Acid amides, after being sufficiently stirred, depart from magnetic agitation, add 0.4 g Fe3O4Particle is simultaneously well mixed.
（2）Prepare oil phase：Weigh 2.63 g OP-4 and 12.37 g SPAN80 to add in 150 mL atoleines, stirring Uniformly, oil phase is made；
（3）Oil phase is moved into three-necked flask, 45 DEG C of heating water baths, maintaining nitrogen purge, stirred by the rpm of rotating speed 450, will Aqueous phase is added dropwise in oil phase, is added 8.8 mL initiator solutions after stirring 0.5 h, is reacted 3 h.
Initiator solution is prepared in advance：Accurately weigh 3.65 g ammonium persulfates and 2.01 g sodium sulfites are dissolved in 20 mL In water, constant volume in 100 mL volumetric flasks is then moved into.
（4）Reaction separates from emulsion product with magnetic force after terminating, then with absolute ethyl alcohol and acetone alternately washing 3 It is secondary, it is put into vacuum drying chamber at 60 DEG C and dries afterwards, had both can obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 286 nm, polydispersity index（PDI）For 0.23, saturation magnetic Change intensity is 10 emu/g.
Embodiment 5
The pretreatment of manioc waste：The former manioc waste after 50 g are crushed is weighed, 3 h is handled through mechanical ball mill, adds 1 L mass Fraction is in 2% NaOH solution, the h of water-bath boiling 10 at 75 DEG C, filter residue crushed after being dried at 70 DEG C is taken after filtering, both Pretreated manioc waste.
Fe3O4The preparation of particle：Measure the FeCl that concentration is 0.5 mol/L3The mL of solution 500 and concentration are 0.5 mol/L FeCl2The mL of solution 285.7 mixing keeps 400 rpm rotating speed mechanical agitation, adds 25 wt% after 85 DEG C of heating water baths Ammoniacal liquor to solution PH is 9.5, and neutrality is washed to after curing 3 h, finally in 60 DEG C of vacuum drying, both obtains Fe3O4Particle.
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Accurately weigh 0.35 g NaOH to be dissolved in 1.5 mL water, add the pretreated wood of 0.1 g Potato, the magnetic agitation in ice-water bath, the methyl methacrylate aqueous solution that 3.5 mL mass fractions are 1% is added, stirs 0.5 h After add 3.5 mL acrylic acid, be further continued for adding 0.5 g acrylamides and 0.018 g N, N '-methylene-bisacrylamide, fill After dividing stirring, depart from magnetic agitation, add 0.4 g Fe3O4Particle is simultaneously well mixed.
（2）Prepare oil phase：Weigh 2.63 g OP-4 and 12.37 g SPAN80 to add in 150 mL atoleines, stirring Uniformly, oil phase is made；
（3）Oil phase is moved into three-necked flask, 45 DEG C of heating water baths, maintaining nitrogen purge, stirred by the rpm of rotating speed 600, will Aqueous phase is added dropwise in oil phase, is added 1.5 mL initiator solutions after stirring 0.5 h, is reacted 10 h.
Initiator solution is prepared in advance：Accurately weigh 3.65 g ammonium persulfates and 2.01 g sodium sulfites are dissolved in 20 mL In water, constant volume in 100 mL volumetric flasks is then moved into.
（4）Reaction separates from emulsion product with magnetic force after terminating, then with absolute ethyl alcohol and acetone alternately washing 3 It is secondary, it is put into vacuum drying chamber at 70 DEG C and dries afterwards, had both can obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 251nm, polydispersity index（PDI）For 0.15, saturation magnetic Change the emu/g of intensity 13.
Embodiment 6
The pretreatment of manioc waste：The former manioc waste after 50 g are crushed is weighed, 1.5 h is handled through mechanical ball mill, adds 1 L matter Measure in the NaOH solution that fraction is 3%, the h of water-bath boiling 6 at 95 DEG C, filter residue crushed after being dried at 90 DEG C is taken after filtering, both Obtain pretreated manioc waste.
Fe3O4The preparation of particle：Measure the FeCl that concentration is 0.5 mol/L3The mL of solution 500 and concentration are 0.5 mol/L FeCl2The mL of solution 285.7 mixing keeps 300 rpm rotating speed mechanical agitation, adds 25 wt% after 75 DEG C of heating water baths Ammoniacal liquor to solution PH is 9.5, and neutrality is washed to after curing 2.5h, finally in 70 DEG C of vacuum drying, both obtains Fe3O4Particle.
The preparation method of the manioc waste magnetic microsphere of the present invention, it comprises the following steps：
（1）Prepare aqueous phase：Accurately weigh 0.117 g NaOH to be dissolved in 5 mL water, add the pretreated wood of 0.4 g Potato slag, the magnetic agitation in ice-water bath, it is water-soluble that the methyl methacrylate that 1.67 mL mass fractions are 1% is added after cooling Liquid, 0.5 mL acrylic acid is added dropwise after stirring 0.5 h, is further continued for adding 3.5 g acrylamides and 0.004 g N, N '-methylene Base bisacrylamide, after being sufficiently stirred, depart from magnetic agitation, add 0.4 g Fe3O4Particle is simultaneously well mixed.
（2）Prepare oil phase：Weigh 2.63 g OP-4 and 12.37 g SPAN80 to add in 150 mL atoleines, stirring Uniformly, oil phase is made；
（3）Oil phase is moved into three-necked flask, 45 DEG C of heating water baths, maintaining nitrogen purge, stirred by rotating speed 600rpm, will Aqueous phase is added dropwise in oil phase, is added 0.55 mL initiator solutions after stirring 0.5 h, is reacted 8 h.
Initiator solution is prepared in advance：Accurately weigh 3.65 g ammonium persulfates and 2.01 g sodium sulfites are dissolved in 20 mL In water, constant volume in 100 mL volumetric flasks is then moved into.
（4）Reaction separates from emulsion product with magnetic force after terminating, then with absolute ethyl alcohol and acetone alternately washing 3 It is secondary, it is put into vacuum drying chamber at 65 DEG C and dries afterwards, had both can obtain manioc waste magnetic microsphere.
Manioc waste magnetic microsphere particle diameter prepared by the present invention is 193nm, polydispersity index（PDI）For 0.18, saturation magnetic Change intensity is 11 emu/g.

Claims (9)

  1. A kind of 1. preparation method of manioc waste magnetic microsphere, it is characterised in that：It comprises the following steps：
    Prepare aqueous phase：Pretreated manioc waste and NaOH are added to the water stirring, monomer first is added after being cooled down under ice-water bath Base methyl acrylate, continue to be stirred, then it is 1 that manioc waste and the mass ratio of acrylic acid, which is added dropwise,:0.625 ~ 35 monomer third Olefin(e) acid；Monomeric acrylamide, crosslinking agent and Fe are continuously added after cooling3O4Particle；
    The addition of methyl methacrylate is 1 with manioc waste mass ratio: 8~27；The addition and propylene of the acrylamide The addition mass ratio of acid is 7: 1~50；
    The pretreatment of manioc waste is：After raw material manioc waste is pulverized and sieved, 0.5-4 h are handled through mechanical ball mill, add quality point Number is in 1% ~ 5% NaOH solution, the h of boiling 3 ~ 12 at 70 ~ 100 DEG C, is filtered, powder after taking filter residue dry at 40 ~ 90 DEG C It is broken, that is, obtain pretreated manioc waste；
    Prepare oil phase：It is 1 according to emulsifying agent and atoleine mass ratio:Emulsifying agent is added to atoleine by 8 ~ 10 proportioning In be made oil phase；
    The maintaining nitrogen purge into oil phase, 45 ~ 55 DEG C of heating water baths, stirring, aqueous phase is added drop-wise in oil phase, adds and trigger after stirring Agent, react 3 ~ 12h；
    React product Magnetic Isolation after terminating, then alternately washed with absolute ethyl alcohol and acetone, then be dried in vacuo, you can To manioc waste magnetic microsphere.
  2. 2. the preparation method of manioc waste magnetic microsphere according to claim 1, it is characterised in that：The manioc waste and NaOH Mass ratio be 1: 1~9；The dosage of crosslinking agent is the 0.1% ~ 8% of monomer gross mass；The Fe3O4The matter of particle and manioc waste Amount is than being 4: 1~16.
  3. 3. the preparation method of manioc waste magnetic microsphere according to claim 1 or 2, it is characterised in that：The crosslinking agent is N, N '-methylene-bisacrylamide.
  4. 4. the preparation method of manioc waste magnetic microsphere according to claim 1, it is characterised in that：The initiator is over cure Sour ammonium and sodium sulfite, the addition of ammonium persulfate are the 0.5% ~ 2% of monomer gross mass, mole of ammonium persulfate and sodium sulfite Than for 1:1.
  5. 5. the preparation method of manioc waste magnetic microsphere according to claim 1, it is characterised in that：The step（1）In Fe3O4The preparation method of particle is：By FeCl3And FeCl2In molar ratio 1.75 ~ 2:1 is added to the water, at 70 ~ 90 DEG C Heating water bath, the stirring of 200 ~ 500 rpm rotating speeds is kept, adding ammoniacal liquor makes solution ph be washed to 9 ~ 10 after curing 2 ~ 4 h Neutrality, at last 40 ~ 70 DEG C vacuum drying can obtain Fe3O4Particle.
  6. 6. the preparation method of manioc waste magnetic microsphere according to claim 1, it is characterised in that：The emulsifying agent is OP-4 With SPAN80 mixture, mixing quality ratio is 1: 1.75~6.
  7. 7. the preparation method of manioc waste magnetic microsphere according to claim 1, it is characterised in that：The step（3）Aqueous phase It is added in oil phase, the volume ratio of aqueous phase addition and atoleine is 1: 5~15.
  8. 8. the preparation method of manioc waste magnetic microsphere according to claim 1, it is characterised in that：The step（4）It is anhydrous Ethanol and acetone alternately washing 3 ~ 5 times, are dried in vacuo at 30 ~ 80 DEG C, produce manioc waste magnetic microsphere.
  9. 9. the manioc waste magnetic microsphere that the preparation method of the manioc waste magnetic microsphere as described in claim 1 ~ 8 is any obtains, its It is characterised by：Manioc waste magnetic microsphere particle diameter is 180~300 nm, polydispersity index（PDI）For 0.14 ~ 0.25, microballoon Saturation magnetization intensity is 10 ~ 21 emu/g.
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