CN108636379A - A kind of positively charged polystyrene microsphere and its preparation method and application - Google Patents
A kind of positively charged polystyrene microsphere and its preparation method and application Download PDFInfo
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention belongs to high molecular polymer field, a kind of positively charged polystyrene microsphere and its preparation method and application is related generally to.Invention uses dispersion copolymerization method, and polystyrene microsphere is prepared by monomer polymerization of styrene, and by the mixed acid nitrification with the concentrated sulfuric acid and concentrated nitric acid preparation, nitro is connected on the phenyl ring of polystyrene microsphere；Again in absolute ethyl alcohol system, use sodium borohydride that nitro is reduced into amino as reducing agent；Then react amino and glycidyltrimetiiylammonium ammonium chloride, positive electricity reagent is connected on amino, positive charge is introduced to Surfaces of Polystyrene Microparticles, pass through the attraction between charged particle, the negatively charged pollutant of low concentration in water is set to be adsorbed to microsphere surface, by high speed centrifugation or it is separated by filtration microballoon again, to achieve the purpose that purified treatment water.Micron order polystyrene microsphere prepared by the present invention can wash desorption with sodium hydroxide, realize the recycling of microballoon.
Description
Technical field
The invention belongs to high molecular polymer fields, and in particular to a kind of positively charged polystyrene microsphere and preparation method thereof
And application.
Background technology
In numerous high molecular materials, polystyrene microsphere is because its rigidity is big, high mechanical strength, acid and alkali-resistance, chemical property
Stablize the features such as and be concerned.Wherein its Materials Styrene is resourceful, cheap, and polystyrene microsphere have than
Surface area is big, particle size is uniform and the properties such as controllable.The preparation method of polystyrene microsphere is generally divided into emulsion polymerization, divides
Dissipate polymerization, seeded polymerization.The polystyrene microsphere grain size that wherein prepared by emulsion polymerization is smaller, generally nanoscale,
Relative difficult when carrying out function modified；Seeded polymerization prepares polystyrene microsphere complex steps, needs to carry out secondary swelling system
It is standby, but polystyrene microsphere particle diameter distribution prepared by the method is extensive；Dispersion copolymerization method preparation process is simple, the polyphenyl second of preparation
Alkene microspherulite diameter also can reach micron order, and functional modification is also relatively easy.Since Surfaces of Polystyrene Microparticles is without functionality
Group, hydrophobicity is too strong, it is difficult to it is compatible with other materials, limit the application of polystyrene microsphere in other respects.It is poly- at present
There are mainly three types of methods for the functionalization of phenylethylene micro ball：First, utilizing the phenyl ring of styrene；Second is that utilizing phenylethylene micro ball remnants
Suspension ethylene double bond；Third, being copolymerized using the monomer with particular functional group.Changed by the functionalization to polystyrene microsphere
Property can enhance it with the bioactive substance such as immobilization of enzyme, protein or to the adsorption treatment of heavy metal ion.
Currently, the heavy metal in drinking water, is mainly carried out by the methods of the other activated carbon of grade, ion exchange resin
The problems such as processing, it is slow that there are adsorption rate, and exchange capacity is small, and effect is limited, and it is not suitable for large-scale water process.And at present
Most of absorption means are adsorbed mainly for the cation of heavy metal, such as Pb2+、Cu2+、Zn2+Plasma, but to Mr. Yu
The acid group of a little heavy metals, such as Cr2O7 2-、CrO4 -、MnO4 -And certain pollutant such as H for causing body eutrophication2PO4 -、
HPO4 2-、PO4 3-Equal anion, the electronegative dyestuff of also certain polluted-waters is such as Congo red, current most of absorption hand
Section is all helpless, is unable to negatively charged anion in selective absorption water, purifying water effect is not excellent enough.
Invention content
In order to solve the disadvantage that the prior art and shortcoming, primary and foremost purpose of the present invention are to provide a kind of positively charged polyphenyl second
Alkene microballoon.
Another object of the present invention is to provide the preparation method of above-mentioned positively charged polystyrene microsphere.
Another object of the present invention is to provide the application of above-mentioned positively charged polystyrene microsphere.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of positively charged polystyrene microsphere, which is characterized in that include the following steps：
(1) preparation of polystyrene microsphere：Dispersant is added in absolute ethyl alcohol, ultrasonic disperse, stirs and fills protection
Gas excludes the air in reaction system, is warming up to 70~78 DEG C, and styrene monomer and initiator is then added, in stirring speed
Under the conditions of 300~600rpm of rate reaction 16~for 24 hours, by product centrifuge washing, vacuum drying, products therefrom is denoted as PS microballoons；
(2) preparation of nitro polystyrene microsphere：PS microballoons made from step (1) are added to the concentrated sulfuric acid and concentrated nitric acid group
At nitration mixture in, ultrasonic disperse stirs evenly and reacts 3~6h under the conditions of 45~65 DEG C, the mixed liquor after reaction is spent
Ionized water dilutes, and filters and cleans drying, and products therefrom is denoted as PS-NO2Microballoon；
(3) preparation of aminopolystyrene microballoon：By PS-NO made from step (2)2Microballoon is added in absolute ethyl alcohol,
Ultrasonic disperse obtains dispersion liquid；Absolute ethyl alcohol is separately taken again, and sodium borohydride and ammonium sulfate are dissolved into absolute ethyl alcohol and is poured into point
Hybrid reaction in dispersion liquid, autoreaction start to add a sodium borohydride every 6~10h, be stirred at 50~70 DEG C
And 24~48h is reacted, deionized water dilution is added after completion of the reaction, filtering is cleaned and is dried for standby, and products therefrom is denoted as PS-NH2
Microballoon；
(4) preparation of positively charged polystyrene microsphere：By PS-NH made from step (3)2Microballoon is scattered in deionized water
In, perchloric acid solution is added dropwise, adds glycidyltrimetiiylammonium ammonium chloride, adds a glycidyl front three every 8~10h
Ammonium chloride adds a perchloric acid solution every 3~4h, 36~48h is stirred evenly and reacted at 80~100 DEG C, then spend
Ionized water centrifugation is cleaned, is dried.
Preferably, the dispersant is polyvinylpyrrolidone, and the initiator is azodiisobutyronitrile.
Preferably, the volume of absolute ethyl alcohol is 3~5 times of styrene monomer volume in step (1), and the dosage of dispersant accounts for
The 2.0~5.0% of styrene monomer quality, the dosage of initiator account for the 0.4~1.2% of styrene monomer quality.
Preferably, which is characterized in that the protective gas described in step (1) is inert gas or nitrogen.
Preferably, a concentration of 98wt% of step (2) described concentrated sulfuric acid, a concentration of 65wt% of concentrated nitric acid, the concentrated sulfuric acid with
Concentrated nitric acid is by sour mass ratio 1.2~1.8:The proportioning of 1 proportions, PS microballoons and nitration mixture is 1:20~50g/mL.
Preferably, solvent is absolute ethyl alcohol, PS-NO in step (3) reaction system2Microballoon and absolute ethyl alcohol in reaction system
The proportioning of total amount is 1:30~1:50g/mL；Ammonium sulfate quality accounts for the 0.2%~0.6% of reaction system absolute ethyl alcohol gross mass,
Add the quality and PS-NO of sodium borohydride every time2Microspheres quality ratio is 1:2~5.
Preferably, PS-NH in step (4)2Microballoon is scattered in deionized water, PS-NH2The ratio of microballoon and deionized water
It is 1:40~100g/mL.
Preferably, step (4) is described adds glycidyltrimetiiylammonium ammonium chloride and PS-NH every time2The proportioning of microballoon is
1:1~2mL/g, a concentration of 5wt%~20wt% of perchloric acid solution, the quality for adding perchloric acid solution every time account in system
The 0.02%~0.05% of deionized water quality.
Positively charged polystyrene microsphere prepared by the preparation method of above-mentioned positively charged polystyrene microsphere.
Application of the above-mentioned positively charged polystyrene microsphere in going water removal in negatively charged pollutant.
Preferably, positively charged polystyrene microsphere Cr in going water removal2O7 2-, H2PO4 -With it is Congo red in application.
Step (1) styrene monomer aggregates into polystyrene microsphere, and crucial governing factor is stirring, needs to close using size
Suitable agitating paddle (cannot use magnetic stir bar, uneven) stirs under constant higher rotation speed, keeps whole system high speed turbulence mixed
It closes uniform, the PS microballoons of uniform particle diameter is aggregated under uniform shear stress.
Step (2) is to connect the nitration reaction of nitro on phenyl ring, key factor be reaction temperature and time, can be relatively low
The reaction was complete in temperature and short period, and too high temperature or too long reaction time can all destroy spherical structure, reaction one
It can be diluted to after the section time in deionized water and terminate reaction.
Step (3) nitro is reduced into amino, is happened at the surface of microballoon, is less than polystyrene in absolute ethyl alcohol in temperature
Glass transition temperature, reducing agent and catalyst excess, under the conditions of the time is sufficiently long, key factor is prepared by step (1)
PS microballoons relative surface area, relative surface area is bigger, and the amino for restoring generation is more.
Step (4) is that amino is reacted with positive electricity reagent GTCA, and between temperature is in 80~100 DEG C, GTCA is excessive, reaction
Under the conditions of time is sufficiently long, the amino of step (3) reduction gained is limiting factor.
The reaction mechanism of the present invention：(1) pass through the polystyrene microsphere of dispersion copolymerization method synthesizing micron-grade；(2) with dense sulphur
Acid and concentrated nitric acid are made into mixed acid nitrification, and nitro is connected on the phenyl ring of polystyrene microsphere；(3) boron is used under the catalysis of ammonium sulfate
Nitro is reduced into amino by sodium hydride in alcohol system；(4) glycidyl three is added in the aqueous solution that perchloric acid adjusts pH
Ammonio methacrylate (GTCA), allows GTCA to be reacted with the amino on microballoon, makes functional group on PS microballoon bands, positive charge is introduced to
Surfaces of Polystyrene Microparticles, so that it is carried electropositive in aqueous solution is made low dense in water by the attraction between charged particle
The negatively charged pollutant of degree is adsorbed to microsphere surface, then by high speed centrifugation or is separated by filtration microballoon, to reach purified treatment
The purpose of water.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) positively charged polystyrene microsphere prepared by the present invention can adsorb the electronegative pollutant in water, big at present
Partial adsorbates agent can only adsorb the pollutants such as positively charged heavy metal ion, the present invention and the suction that can only adsorb positively charged pollutant
Attached dose is used in combination and can reach better water treatment efficiency.
(2) the positively charged polystyrene microsphere for preparing of the present invention, large specific surface area remove negatively charged pollutant in water
It removes, has the characteristics that adsorption capacity is larger, processing speed is fast, can be in 10min, the negatively charged pollutant in quick adsorption water.
There is good advantage in terms of the emergency processing of drinking water and the negatively charged pollutant of industrial wastewater.
(3) positively charged polystyrene microsphere prepared by the present invention can wash desorption with sodium hydroxide, reuse.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of polystyrene microsphere prepared by 1 step of embodiment (1).
Fig. 2 is the scanning electron microscope (SEM) photograph of nitro polystyrene microsphere prepared by 1 step of embodiment (2).
Fig. 3 is the scanning electron microscope (SEM) photograph of aminopolystyrene microballoon prepared by 1 step of embodiment (3).
Fig. 4 is the scanning electron microscope (SEM) photograph of positively charged polystyrene microsphere prepared by 1 step of embodiment (4).
Fig. 5 is the dynamic curve diagram of positively charged polystyrene microsphere adion prepared by 1 step of embodiment (4).
Fig. 6 is the removal rate figure of positively charged polystyrene microsphere adion prepared by 1 step of embodiment (4).
Fig. 7 is the saturation of positively charged polystyrene microsphere prepared by 1 step of embodiment (4) and Powdered Activated Carbon to anion
The comparison of adsorbance.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1：
(1) preparation of polystyrene microsphere：2g polyvinylpyrrolidones (PVP-30) are added to and fill the anhydrous second of 200mL
In the three-necked flask of alcohol, ultrasonic disperse stirs simultaneously nitrogen filled protection 30min, is warming up to 75 DEG C, and 50mL styrene is added and 0.4g is even
Nitrogen bis-isobutyronitrile (AIBN) reacts for 24 hours under the conditions of stir speed (S.S.) 500rmp, and products therefrom is clean with absolute ethyl alcohol centrifuge washing,
It is dried in vacuo for 24 hours under the conditions of 50 DEG C again, products therefrom is denoted as PS microballoons.
(2) preparation of nitro polystyrene microsphere：With the concentrated nitric acid of the concentrated sulfuric acid of 98wt% and 65wt% in mass ratio=
1.5:1 prepares nitration mixture, PS microballoons made from 3g steps (1) is poured into single neck flask equipped with 120mL nitration mixture, ultrasonic disperse,
60 DEG C of reaction 4h are warming up to being sufficiently stirred lower oil bath, the mixed liquor after reaction is diluted in the deionized water of 400mL, is filtered
And be washed with deionized totally, then be dried in vacuo for 24 hours under the conditions of 50 DEG C, products therefrom is denoted as PS-NO2Microballoon.
(3) preparation of aminopolystyrene microballoon：Take PS-NO made from 3g steps (2)2Microballoon is in the mono- neck flasks of 250mL
In, 60mL absolute ethyl alcohol ultrasonic disperses are added, another to weigh 1.0g sodium borohydrides, it is anhydrous that 60mL is added in beaker in 0.3g ammonium sulfate
Ethyl alcohol is fully dissolved in beaker, and flask is added in the solution in beaker, 60 DEG C are warming up in the case where being sufficiently stirred, was mended every 10 hours
Add 1.0g sodium borohydrides, after reacting 48h, be slowly added to deionized water and White Flocculus occur, continuously adds deionized water to wadding
Shape object is completely dissolved, and filtering is cleaned, then is dried in vacuo for 24 hours under the conditions of 50 DEG C, and products therefrom is denoted as PS-NH2Microballoon.
(4) preparation of positively charged polystyrene microsphere：Take PS-NH made from 2g steps (3)2Microballoon is burnt in the mono- necks of 250mL
In bottle, 100mL deionized waters are added, and the perchloric acid solution of 0.3mL 10wt%, the glycidol of 1.0mL 80wt% is added
Base trimethyl ammonium chloride (GTCA) solution, oil bath are warming up to 90 DEG C of reaction 48h, the perchloric acid of 0.3mL10wt% are added every 3h
The GTCA solution of 1.0mL 80wt% is added every 10h in solution, takes out after reaction product deionized water centrifuge washing 4 times, then
It is dried in vacuo for 24 hours under the conditions of 50 DEG C, obtains the positively charged polystyrene microsphere powder of yellow.
Embodiment 2：
(1) preparation of polystyrene microsphere：2g polyvinylpyrrolidones (PVP-30) are added to and fill the anhydrous second of 200mL
In the three-necked flask of alcohol, ultrasonic disperse stirs simultaneously nitrogen filled protection 30min, is warming up to 78 DEG C, and 50mL styrene is added and 0.5g is even
Nitrogen bis-isobutyronitrile (AIBN) reacts 20h under the conditions of stir speed (S.S.) 600rmp, and products therefrom is clean with absolute ethyl alcohol centrifuge washing,
It is dried in vacuo 20h under the conditions of 40 DEG C again, obtains the PS microsphere powders of white.
(2) preparation of nitro polystyrene microsphere：With the concentrated nitric acid of the concentrated sulfuric acid of 98wt% and 65wt% in mass ratio=
1.6:1 prepares nitration mixture, PS microballoons made from 3g steps (1) is poured into single neck flask equipped with 100mL nitration mixture, ultrasonic disperse,
55 DEG C of reaction 5h are warming up to being sufficiently stirred lower oil bath, the mixed liquor after reaction is diluted in the deionized water of 500mL, is filtered
And be washed with deionized totally, then it is dried in vacuo 20h under the conditions of 40 DEG C, obtain flaxen PS-NO2Microsphere powder.
(3) preparation of aminopolystyrene microballoon：Take PS-NO made from 3g steps (2)2Microballoon is in the mono- neck flasks of 250mL
In, 60mL absolute ethyl alcohol ultrasonic disperses are added, another to weigh 1.0g sodium borohydrides, it is anhydrous that 60mL is added in beaker in 0.3g ammonium sulfate
Ethyl alcohol is fully dissolved in beaker, and flask is added in the solution in beaker, 55 DEG C are warming up in the case where being sufficiently stirred, was mended every 8 hours
Add 1.0g sodium borohydrides, after reacting 48h, be slowly added to deionized water and White Flocculus occur, continuously adds deionized water to wadding
Shape object is completely dissolved, and filtering is cleaned, then is dried in vacuo 20h under the conditions of 50 DEG C, obtains filemot PS-NH2Microsphere powder.
(4) preparation of positively charged polystyrene microsphere：Take PS-NH made from 2g steps (3)2Microballoon is burnt in the mono- necks of 250mL
In bottle, 100mL deionized waters are added, and the perchloric acid solution of 0.3mL 10wt%, the glycidol of 1.0mL 80wt% is added
Base trimethyl ammonium chloride (GTCA) solution, oil bath are warming up to 100 DEG C of reaction 48h, the high chlorine of 0.42mL 10wt% are added every 3h
The GTCA solution of 1.0mL 80wt% is added every 8h in acid solution, takes out and uses deionized water centrifuge washing 4 times, then in 50 DEG C of items
It is dried in vacuo 16h under part, obtains the positively charged polystyrene microsphere powder of yellow.
Embodiment 3：
(1) preparation of polystyrene microsphere：2g polyvinylpyrrolidones (PVP-30) are added to and fill the anhydrous second of 200mL
In the three-necked flask of alcohol, ultrasonic disperse stirs simultaneously nitrogen filled protection 30min, is warming up to 70 DEG C, and 50mL styrene is added and 0.3g is even
Nitrogen bis-isobutyronitrile (AIBN) reacts 20h under the conditions of stir speed (S.S.) 500rmp, and products therefrom is clean with absolute ethyl alcohol centrifuge washing,
It is dried in vacuo 20h under the conditions of 50 DEG C again, obtains the PS microsphere powders of white.
(2) preparation of nitro polystyrene microsphere：With the concentrated nitric acid of the concentrated sulfuric acid of 98wt% and 65wt% in mass ratio=
1.2:1 prepares nitration mixture, PS microballoons made from 3g steps (1) is poured into single neck flask equipped with 120mL nitration mixture, ultrasonic disperse,
50 DEG C of reaction 6h are warming up to being sufficiently stirred lower oil bath, the mixed liquor after reaction is diluted in the deionized water of 500mL, is filtered
And be washed with deionized totally, then be dried in vacuo for 24 hours under the conditions of 30 DEG C, obtain flaxen PS-NO2Microsphere powder.
(3) preparation of aminopolystyrene microballoon：Take PS-NO made from 3g steps (2)2Microballoon is in the mono- neck flasks of 250mL
In, 70mL absolute ethyl alcohol ultrasonic disperses are added, another to weigh 1.2g sodium borohydrides, it is anhydrous that 70mL is added in beaker in 0.3g ammonium sulfate
Ethyl alcohol is fully dissolved in beaker, and flask is added in the solution in beaker, 55 DEG C are warming up in the case where being sufficiently stirred, was mended every 10 hours
Add 1.2g sodium borohydrides, after reacting 48h, be slowly added to deionized water and White Flocculus occur, continuously adds deionized water to wadding
Shape object is completely dissolved, and filtering is cleaned, then is dried in vacuo for 24 hours under the conditions of 40 DEG C, and filemot PS-NH is obtained2Microsphere powder.
(4) preparation of positively charged polystyrene microsphere：Take PS-NH made from 2g steps (3)2Microballoon is burnt in the mono- necks of 250mL
In bottle, 100mL deionized waters are added, and the perchloric acid solution of 0.3mL 10wt%, the glycidol of 1.0mL 80wt% is added
Base trimethyl ammonium chloride (GTCA) solution, oil bath are warming up to 80 DEG C of reaction 48h, the perchloric acid of 0.35mL10wt% are added every 4h
The GTCA solution of 1.0mL 80wt% is added every 8h in solution, takes out and uses deionized water centrifuge washing 4 times, then in 40 DEG C of conditions
Lower vacuum drying for 24 hours, obtains the positively charged polystyrene microsphere powder of yellow.
Embodiment 4：
(1) preparation of polystyrene microsphere：2g polyvinylpyrrolidones (PVP-30) are added to and fill the anhydrous second of 200mL
In the three-necked flask of alcohol, ultrasonic disperse stirs simultaneously nitrogen filled protection 30min, is warming up to 76 DEG C, and 50mL styrene is added and 0.3g is even
Nitrogen bis-isobutyronitrile (AIBN) reacts 16h under the conditions of stir speed (S.S.) 480rmp, and products therefrom is clean with absolute ethyl alcohol centrifuge washing,
The PS microsphere powders for obtaining white for 24 hours are dried in vacuo under the conditions of 40 DEG C again.
(2) preparation of nitro polystyrene microsphere：With the concentrated nitric acid of the concentrated sulfuric acid of 98wt% and 65wt% in mass ratio=
1.5:1 prepares nitration mixture, PS microballoons made from 3g steps (1) is poured into single neck flask equipped with 110mL nitration mixture, ultrasonic disperse,
50 DEG C of reaction 4h are gradually heating to being sufficiently stirred lower oil bath, the mixed liquor after reaction is diluted in the deionized water of 500mL,
It filters and is washed with deionized totally, then 12h is dried in vacuo under the conditions of 60 DEG C, obtain flaxen PS-NO2Microballoon powder
End.
(3) preparation of aminopolystyrene microballoon：Take PS-NO made from 3g steps (2)2Microballoon is in the mono- neck flasks of 250mL
In, 60mL absolute ethyl alcohol ultrasonic disperses are added, another to weigh 1.2g sodium borohydrides, it is anhydrous that 60mL is added in beaker in 0.4g ammonium sulfate
Ethyl alcohol is fully dissolved in beaker, and flask is added in the solution in beaker, 65 DEG C are warming up in the case where being sufficiently stirred, was mended every 10 hours
Add 1.2g sodium borohydrides, after reacting 48h, be slowly added to deionized water and White Flocculus occur, continuously adds deionized water to wadding
Shape object is completely dissolved, and filtering is cleaned, then is dried in vacuo 20h under the conditions of 40 DEG C, obtains filemot PS-NH2Microsphere powder.
(4) preparation of positively charged polystyrene microsphere：Take PS-NH made from 2g steps (3)2Microballoon is burnt in the mono- necks of 250mL
In bottle, 100mL deionized waters are added, and the perchloric acid solution of 0.4mL 10wt%, the glycidol of 1.2mL 80wt% is added
Base trimethyl ammonium chloride (GTCA) solution, oil bath are warming up to 95 DEG C of reaction 42h, the perchloric acid of 0.4mL10wt% are added every 4h
The GTCA solution of 1.2mL 80wt% is added every 10h in solution, takes out and uses deionized water centrifuge washing 4 times, then in 40 DEG C of conditions
Lower vacuum drying 12h obtains the positively charged polystyrene microsphere powder of yellow.
Embodiment 5：
(1) preparation of polystyrene microsphere：2g polyvinylpyrrolidones (PVP-30) are added to and fill the anhydrous second of 200mL
In the three-necked flask of alcohol, ultrasonic disperse stirs simultaneously nitrogen filled protection 30min, is warming up to 73 DEG C, and 50mL styrene is added and 0.5g is even
Nitrogen bis-isobutyronitrile (AIBN) reacts 22h under the conditions of stir speed (S.S.) 560rmp, and products therefrom is clean with absolute ethyl alcohol centrifuge washing,
It is dried in vacuo 16h under the conditions of 50 DEG C again, obtains the PS microsphere powders of white.
(2) preparation of nitro polystyrene microsphere：With the concentrated nitric acid of the concentrated sulfuric acid of 98wt% and 65wt% in mass ratio=
1.6:1 prepares nitration mixture, PS microballoons made from 3g steps (1) is poured into single neck flask equipped with 120mL nitration mixture, ultrasonic disperse,
60 DEG C of reaction 3h are warming up to being sufficiently stirred lower oil bath, the mixed liquor after reaction is diluted in the deionized water of 500mL, is filtered
And be washed with deionized totally, then it is dried in vacuo 16h under the conditions of 50 DEG C, obtain flaxen PS-NO2Microsphere powder.
(3) preparation of aminopolystyrene microballoon：Take PS-NO made from 3g steps (2)2Microballoon is in the mono- neck flasks of 250mL
In, 50mL absolute ethyl alcohol ultrasonic disperses are added, another to weigh 1.2g sodium borohydrides, it is anhydrous that 50mL is added in beaker in 0.4g ammonium sulfate
Ethyl alcohol is fully dissolved in beaker, and flask is added in the solution in beaker, be sufficiently stirred it is lower be gradually warming up to 60 DEG C, it is small every 8
When add 1.2g sodium borohydrides, after reacting 40h, be slowly added to deionized water and White Flocculus occur, continuously add deionized water
It is completely dissolved to floccule, filtering is cleaned, then is dried in vacuo for 24 hours under the conditions of 40 DEG C, and filemot PS-NH is obtained2Microballoon powder
End.
(4) preparation of positively charged polystyrene microsphere：Take PS-NH made from 2g steps (3)2Microballoon is burnt in the mono- necks of 250mL
In bottle, 100mL deionized waters are added, and the perchloric acid solution of 0.3mL 10wt%, the glycidyl of 1.0mL 80% is added
Trimethyl ammonium chloride (GTCA) solution, oil bath are warming up to 88 DEG C of reaction 42h, and the perchloric acid that 0.3mL10wt% is added every 3h is molten
The GTCA solution of 1.0mL 80wt% is added every 8h in liquid, takes out and uses deionized water centrifuge washing 4 times, then under the conditions of 60 DEG C
It is dried in vacuo 12h, obtains the positively charged polystyrene microsphere powder of yellow.
Embodiment 6：
(1) preparation of polystyrene microsphere：2g polyvinylpyrrolidones (PVP-30) are added to and fill the anhydrous second of 200mL
In the three-necked flask of alcohol, ultrasonic disperse stirs simultaneously nitrogen filled protection 30min, is warming up to 75 DEG C, and 50mL styrene is added and 0.4g is even
Nitrogen bis-isobutyronitrile (AIBN) reacts 22h under the conditions of stir speed (S.S.) 520rmp, and products therefrom is clean with absolute ethyl alcohol centrifuge washing,
It is dried in vacuo 12h under the conditions of 60 DEG C again, obtains the PS microsphere powders of white.
(2) preparation of nitro polystyrene microsphere：With the concentrated nitric acid of the concentrated sulfuric acid of 98wt% and 65wt% in mass ratio=
1.4:1 prepares nitration mixture, PS microballoons made from 3g steps (1) is poured into single neck flask equipped with 120mL nitration mixture, ultrasonic disperse,
48 DEG C of reaction 6h are gradually heating to being sufficiently stirred lower oil bath, the mixed liquor after reaction is diluted in the deionized water of 500mL,
It filters and is washed with deionized totally, then 16h is dried in vacuo under the conditions of 40 DEG C, obtain flaxen PS-NO2Microballoon powder
End.
(3) preparation of aminopolystyrene microballoon：Take PS-NO made from 3g steps (2)2Microballoon is in the mono- neck flasks of 250mL
In, 60mL absolute ethyl alcohol ultrasonic disperses are added, another to weigh 1.0g sodium borohydrides, it is anhydrous that 60mL is added in beaker in 0.3g ammonium sulfate
Ethyl alcohol is fully dissolved in beaker, and flask is added in the solution in beaker, 55 DEG C are warming up in the case where being sufficiently stirred, was mended every 10 hours
Add 1.0g sodium borohydrides, after reacting 40h, be slowly added to deionized water and White Flocculus occur, continuously adds deionized water to wadding
Shape object is completely dissolved, and filtering is cleaned, then is dried in vacuo 20h under the conditions of 50 DEG C, obtains filemot PS-NH2Microsphere powder.
(4) preparation of positively charged polystyrene microsphere：Take PS-NH made from 2g steps (3)2Microballoon is burnt in the mono- necks of 250mL
In bottle, 100mL deionized waters are added, and the perchloric acid solution of 0.4mL 10wt%, the glycidol of 1.5mL 80wt% is added
Base trimethyl ammonium chloride (GTCA) solution, oil bath are warming up to 80 DEG C of reaction 48h, the perchloric acid of 0.4mL10wt% are added every 4h
The GTCA solution of 1.5mL 80wt% is added every 10h in solution, takes out and uses deionized water centrifuge washing 4 times, then in 48 DEG C of conditions
Lower vacuum drying 20h obtains the positively charged polystyrene microsphere powder of yellow.
Fig. 1, Fig. 2, Fig. 3, Fig. 4 are respectively PS microballoons, PS-NO prepared by embodiment 12Microballoon, PS-NH2It is microballoon, positively charged
Image of the polystyrene microsphere under scanning electron microscope.The PS microballoon shapes prepared by the visible this method of Fig. 1 are perfectly round spherical shape,
And the grain size of microballoon is than more uniform；Visible after a series of modification by Fig. 2, Fig. 3, Fig. 4, the overall structure of microballoon does not have
It is destroyed, still maintains spherical shape well, only surface roughness changes.
Fig. 5 be embodiment 1 prepare positively charged polystyrene microsphere adsorption concentration is 30mg/L respectively under the conditions of 25 DEG C
Congo red solution, 20mg/L Cr2O7 2-The H of solution, 10mg/L2PO4 -The concentration-time profile of solution.As seen from the figure, above
Several ions adsorb in 10min and basically reach balance, illustrate that adsorption rate is fast, can be used for the fast purification of water.
Fig. 6 is that the positively charged polystyrene microspheres of 30mg prepared by embodiment 1 adsorb 10mL respectively under the conditions of 25 DEG C
The Congo red solution of 20mg/L, the Cr of 5mL 20mg/L2O7 2-Solution, 3mL 10mg/L H2PO4 -The clearance rate figure of solution.By scheming
It is found that positively charged microballoon is for Congo red and Cr2O7 2-Clearance rate it is higher, to H2PO4 -Clearance rate it is then relatively low, explanation
The microballoon is to Cr2O7 2-With good elimination effect.
Fig. 7 is that positively charged polystyrene microsphere prepared by 20mg embodiments 1 is added to 10mL under the conditions of 25 DEG C
In the Congo red solution of 150mg/L, and 20mg Powdered Activated Carbons are added in the Congo red solution of 10mL 150mg/L；It will
Positively charged polystyrene microsphere prepared by 20mg embodiments 1 is added to the Cr of 5mL 150mg/L2O7 2-In solution, and by 20mg
Powdered Activated Carbon is added to the Cr of 5mL 150mg/L2O7 2-The different adsorbents measured in solution inhale the saturation of different anions
The comparison diagram of attached amount.As seen from the figure, positively charged polystyrene microsphere is more than Powdered Activated Carbon to Congo red saturated extent of adsorption, right
Cr2O7 2-Saturated extent of adsorption be even more remote super Powdered Activated Carbon, illustrate that the adsorption capacity of the microballoon is larger.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of positively charged polystyrene microsphere, which is characterized in that include the following steps：
(1) preparation of polystyrene microsphere：Dispersant is added in absolute ethyl alcohol, ultrasonic disperse, stirs and fills protective gas
The air in reaction system is excluded, is warming up to 70~78 DEG C, styrene monomer and initiator is then added, in stir speed (S.S.)
Under the conditions of 300~600rpm reaction 16~for 24 hours, by product centrifuge washing, vacuum drying, products therefrom is denoted as PS microballoons；
(2) preparation of nitro polystyrene microsphere：By PS microballoons made from step (1) be added to the concentrated sulfuric acid and concentrated nitric acid composition
In nitration mixture, ultrasonic disperse stirs evenly and reacts 3~6h under the conditions of 45~65 DEG C, by the mixed liquor deionization after reaction
Water dilutes, and filters and cleans drying, and products therefrom is denoted as PS-NO2Microballoon；
(3) preparation of aminopolystyrene microballoon：By PS-NO made from step (2)2Microballoon is added in absolute ethyl alcohol, ultrasound point
It dissipates, obtains dispersion liquid；Absolute ethyl alcohol is separately taken again, and sodium borohydride and ammonium sulfate are dissolved into absolute ethyl alcohol and is poured into dispersion liquid
Hybrid reaction, autoreaction start to add a sodium borohydride every 6~10h, stir and react at 50~70 DEG C
Deionized water dilution is added in 24~48h after completion of the reaction, and filtering is cleaned and is dried for standby, and products therefrom is denoted as PS-NH2Microballoon；
(4) preparation of positively charged polystyrene microsphere：By PS-NH made from step (3)2Microballoon is scattered in deionized water, is added dropwise
Perchloric acid solution adds glycidyltrimetiiylammonium ammonium chloride, adds a glycidyltrimetiiylammonium chlorination every 8~10h
Ammonium adds a perchloric acid solution every 3~4h, 36~48h is stirred evenly and reacted at 80~100 DEG C, then use deionized water
Centrifugation is cleaned, is dried.
2. the preparation method of positively charged polystyrene microsphere according to claim 1, which is characterized in that the dispersant
For polyvinylpyrrolidone, the initiator is azodiisobutyronitrile.
3. the preparation method of positively charged polystyrene microsphere according to claim 2, which is characterized in that nothing in step (1)
The volume of water-ethanol is 3~5 times of styrene monomer volume, the dosage of dispersant account for styrene monomer quality 2.0~
5.0%, the dosage of initiator accounts for the 0.4~1.2% of styrene monomer quality.
4. according to the preparation method of the positively charged polystyrene microsphere of claims 1 to 3 any one of them, which is characterized in that step
Suddenly a concentration of 98wt% of (2) described concentrated sulfuric acid, a concentration of 65wt% of concentrated nitric acid, the concentrated sulfuric acid press acid in mass ratio with concentrated nitric acid
1.2~1.8:The proportioning of 1 proportions, PS microballoons and nitration mixture is 1:20~50g/mL.
5. the preparation method of positively charged polystyrene microsphere according to claim 1, which is characterized in that step (3) is reacted
Solvent is absolute ethyl alcohol, PS-NO in system2The proportioning of microballoon and absolute ethyl alcohol total amount in reaction system is 1:30~1:50g/
mL；Ammonium sulfate quality accounts for the 0.2%~0.6% of reaction system absolute ethyl alcohol gross mass, adds the quality and PS- of sodium borohydride every time
NO2Microspheres quality ratio is 1:2~5.
6. the preparation method of positively charged polystyrene microsphere according to claim 1, which is characterized in that PS- in step (4)
NH2Microballoon is scattered in deionized water, PS-NH2The ratio of microballoon and deionized water is 1:40~100g/mL.
7. the preparation method of positively charged polystyrene microsphere according to claim 1, which is characterized in that step (4) is described
Add glycidyltrimetiiylammonium ammonium chloride and PS-NH every time2The proportioning of microballoon is 1:1~2mL/g, the perchloric acid solution are dense
Degree be 5wt%~20wt%, add every time perchloric acid solution quality account for deionized water quality in system 0.02%~
0.05%.
8. the preparation method of positively charged polystyrene microsphere according to claim 1, which is characterized in that step (1) is described
Protective gas be inert gas or nitrogen.
9. positively charged polyphenyl second prepared by the preparation method of the positively charged polystyrene microsphere of claim 1~8 any one of them
Alkene microballoon.
10. application of the positively charged polystyrene microsphere in going water removal in negatively charged pollutant described in claim 9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113368691A (en) * | 2021-06-03 | 2021-09-10 | 浙江工业大学 | Preparation method of aramid fiber organic solvent-resistant nanofiltration membrane |
| CN113368691B (en) * | 2021-06-03 | 2022-04-19 | 浙江工业大学 | Preparation method of aramid fiber organic solvent-resistant nanofiltration membrane |
| CN115449345A (en) * | 2022-08-29 | 2022-12-09 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano composite abrasive under microwave condition |
| CN115449345B (en) * | 2022-08-29 | 2023-08-22 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano-composite abrasive under microwave condition |
| CN116549679A (en) * | 2023-07-06 | 2023-08-08 | 北京普尔伟业生物科技有限公司 | Suspension containing radioactive microspheres and preparation method and application thereof |
| CN116549679B (en) * | 2023-07-06 | 2023-10-10 | 北京普尔伟业生物科技有限公司 | Suspension containing radioactive microspheres and preparation method and application thereof |
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