CN104069782B - A kind of preparation method of functionalized polyvinyl alcohol microballoon and application - Google Patents
A kind of preparation method of functionalized polyvinyl alcohol microballoon and application Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and application of functionalized polyvinyl alcohol microballoon, preparation method: polyvinyl alcohol microparticles, epoxychloropropane, hydrochloric acid solution are mixed, stirring in water bath reaction 1-5h, reaction finish rear centrifugal, water is cleaned, dry, for subsequent use; The chloro polyvinyl alcohol microparticles of gained and TBAB, ethylenediamine, sodium hydroxide solution are mixed, stirring in water bath reaction 4-10h, reaction finish rear centrifugal, use ethanol cleaning, drying, for subsequent use; By the amination polyvinyl alcohol microparticles of gained and 2-(2-pyridine) azo resorcinol, formaldehyde, distilled water mix, and under nitrogen, stirs 6-18h, centrifugal after reaction, clean the dry end product that to obtain with ethanol. Functionalized polyvinyl alcohol microballoon provided by the invention has the ability of chelating heavy metal, can be used for detecting and processing divalent heavy metal ions in waste water, has the advantages that preparation condition is simple, with low cost, the detection response time is short, adsorption capacity is large.
Description
Technical field
The invention belongs to waste water and detect and process field, be specifically related to a kind of preparation method of functionalized polyvinyl alcohol microballoonAnd apply in heavy metal polluted waste water detection and adsorption treatment.
Background technology
The toxicity that heavy metal has is very large, and in water body, having excessive heavy metal is all ten to natural environment and healthPoint dangerous. So how detection rapidly and efficiently and the heavy metal of processing in water body are the focuses of present stage research. In recent yearsCome, developed the method for many detection heavy metals, as ultraviolet visible spectrometry, atomic absorption spectrography (AAS), differentiated pulse negative electrode voltPeace method and inductance coupling high atomic spectrometry determination etc., these methods are the heavy metal in working sample fast and accuratelyContent, and measurement range is large. But these methods need high cost and most suitable experiment condition, and a huge sum of moneyBelong to sample preserve and transport in extremely easily loss, so need development a kind of portable, that original place is measured or even canThe method arriving with naked-eye observation is measured Heavy Metals in Waters content. As everyone knows, most of heavy metal ion can with some spyFixed generation coordination chelatropic reaction generates chromophore, and the color that some chromophore produces can arrive by naked-eye observation. ThisSince sample, mensuration heavy metal ion that can be fast and convenient in original place have or not even content range. Similarly, utilize coordination chelaClose also effective heavy-metal ion removal of reaction. It is suitable that absorption method utilizes solid material to adsorb one or more pollutants recyclingSolvent desorbed, thereby reach the object of removal. Sorbing material mainly utilizes Van der Waals force, chelation, ionThe physics chemical action such as exchange, absorption chelating exchange heavy metal ion, has easy operation, the selective advantage such as various.
Polyvinyl alcohol (PVA) under normal temperature is white powder, sheet or cotton-shaped solid, nonpoisonous and tasteless, is widely used, and isA kind of source is sufficient, cheap, the material of safety non-pollution. Moreover its stable in properties, utilizes polyvinyl alcohol to prepareMicroballoon, not only contain huge surface can, Adsorption of Heavy Metals, and can and then modify upper ammonia by series of chemicalBase, carboxyl etc. have the group of powerful chelating ability, even can modify the group with heavy metal coordination colour developing. 2-(2-pyridine) is evenNitrogen resorcinol (PAR) is a kind of common metal developer and extractant, produces red or purplish red with the coordination of divalence heavy metalThe compound of look. Therefore,, by serial chemical reaction, polyvinyl alcohol can be modified to upper 2-(2-pyridine) azo resorcinol groupGroup, thus carry out detection and the removal of divalent heavy metal ions in waste water.
Summary of the invention
The object of this invention is to provide a kind of preparation method of functionalized polyvinyl alcohol microballoon, this functional method success rateHeight, preparation method is simple, and raw material economics is easy to get, and can realize batch production.
Technical scheme: a kind of preparation method of functionalized polyvinyl alcohol microballoon, comprises the steps:
1) chloro of polyvinyl alcohol microparticles: polyvinyl alcohol microparticles, epoxychloropropane, hydrochloric acid solution are mixed, and water-bath is stirredMix reaction 1-5h, bath temperature is 60-100 DEG C, reaction finish rear centrifugal, water clean, dry, for subsequent use;
2) amination of polyvinyl alcohol microparticles: by step 1) chloro polyvinyl alcohol microparticles and the tetrabutyl phosphonium bromide of gainedAmmonium, ethylenediamine, sodium hydroxide solution mix, stirring in water bath reaction 4-10h, bath temperature is 60-100 DEG C, after reaction finishes fromThe heart, use ethanol cleaning, drying, for subsequent use;
3) by step 2) the amination polyvinyl alcohol microparticles of gained and 2-(2-pyridine) azo resorcinol, formaldehyde, distillationWater mixes, and under nitrogen, stirs 6-18h, centrifugal after reaction, clean the dry end product that to obtain with ethanol.
As preferably, step 1) amount ratio of described polyvinyl alcohol microparticles, epoxychloropropane, hydrochloric acid solution is 1g:1-10mL:30-100mL, the pH value of hydrochloric acid solution is 1-5, and speed of agitator is 200-2000rpm, and centrifugal speed is 1000-5000rpm, centrifugation time is 1-10min.
As further preferably, step 1) bath temperature be 80 DEG C, speed of agitator is 500rpm, the stirring reaction time is2h, centrifugation time is 5min, centrifugal speed is 3500rpm.
As further preferably, step 1) amount ratio of described polyvinyl alcohol microparticles, epoxychloropropane, hydrochloric acid solution is1g:4mL:50mL, the pH of hydrochloric acid solution is 2.
As preferably, step 2) described chloro polyvinyl alcohol microparticles, TBAB, ethylenediamine, NaOHThe amount ratio of solution is 1g:0.01-1g:10-50mL:10-50mL, and the pH of sodium hydroxide solution is 9-13, and speed of agitator is200-2000rpm, centrifugal speed is 1000-5000rpm, centrifugation time is 1-10min.
As further preferably, step 2) bath temperature be 80 DEG C, speed of agitator is 500rpm, the stirring reaction time is6h, centrifugation time is 5min, centrifugal speed is 3500rpm.
As further preferred, step 2) described chloro polyvinyl alcohol microparticles, TBAB, ethylenediamine, hydrogenThe amount ratio of sodium hydroxide solution is 1g:0.1g:20mL:20mL, and described sodium hydroxide solution pH is 11.5.
As preferably, step 3) described amination polyvinyl alcohol microparticles, 2-(2-pyridine) azo resorcinol, formaldehyde,The amount ratio of distilled water is 1g:0.1-2g:5-20mL:5-20mL, and speed of agitator is 100-500rpm, and centrifugal speed is 1000-5000rpm, the time is 1-10min.
As further preferred, step 3) be uniformly mixed reaction 12h, speed of agitator (paddle radius is 2cm) is200rpm, centrifugation time is 5min, centrifugal speed is 3500rpm.
As further preferably, step 3) described amination polyvinyl alcohol microparticles and 2-(2-pyridine) azo resorcinol,The amount ratio of formaldehyde, distilled water is 1g:1g:10mL:10mL.
As preferably, step 1), 2), 3) described in centrifugation step, centrifugal rotational speed is 3500rpm, centrifugation time is5min。
The functionalized polyvinyl alcohol microballoon that the present invention prepares contains a large amount of different chelation groups, not only absorption in a large numberHeavy metal ions in wastewater, produces change color but also can react with heavy metal, detects the existence of heavy metal ion.
The application of functionalized polyvinyl alcohol microballoon of the present invention in heavy metal wastewater thereby detects and processes.
Application process is as follows: the functionalized polyvinyl alcohol microballoon preparing is dropped into containing in the waste water of heavy metal, carry outDetect and absorption, after completing, the variation that visually observes color can know that divalent heavy metal ions exists, scanning ultraviolet-visibleSpectrum can be known the scope that heavy metal ion exists.
Because polyvinyl alcohol is with a large amount of hydrability hydroxyls, step 1 of the present invention) the preparation of polyvinyl alcohol microparticles basicBe to utilize inverse suspension crosslinking method, just select reagent difference to some extent.
For example, the ether that is dissolved with glutaraldehyde joins taking polyvinyl alcohol water solution as water, normal heptane is the emulsion of oil phaseMiddle as crosslinking agent, micro-concentrated hydrochloric acid is added drop-wise in emulsion as catalyst, emulsion polymerization is prepared polyvinyl alcohol microparticles (ZhaoGrand celebration, Tan Jinquan. the preparation of polyvinyl alcohol microparticles. Chinese Journal of New Drugs .2005,14 (2): 181-184).
Above-mentioned polyvinyl alcohol microparticles can also be 201210176608.0 by application number, name is called that " immobilization laccase is micro-Ball carrier and preparation method thereof and application " Chinese invention patent application prepare, the particle diameter of the polyvinyl alcohol microparticles obtainingFor 1-50 μ m. Concrete preparation method is: polyethylene alcohol and water is mixed to dissolving in boiling water bath, add liquid stone after cooling againWax and Si Ban 80, add hydrochloric acid solution and glutaraldehyde solution to stir again after stirring at room temperature certain hour, after centrifugation, gatheredVinyl alcohol microballoon.
First the present invention carries out chloro by polyvinyl alcohol microparticles, by epoxychloropropane open loop, and polyvinyl alcohol in connectionHydroxyl, then utilizes the amino chloro that replaces, finally by Mannich reaction, and 2-in connection (2-pyridine) azo resorcinol groupRoll into a ball, make it have the ability of chelating heavy metal, obtain having the polyvinyl alcohol microparticles of colour developing and adsorption function, detect thereby realizeEffect with Adsorption heavy metal ion. The present invention has following beneficial effect:
(1) functional method of polyvinyl alcohol microparticles provided by the invention is simple to operate, preparation condition gentleness;
(2) method of functionalized polyvinyl alcohol microballoon provided by the invention is with low cost;
(3) the functionalized polyvinyl alcohol microballoon that method provided by the invention obtains, can fast detecting to heavy metal ion;
(4) functionalized polyvinyl alcohol microballoon Adsorption of Heavy Metal Ions successful provided by the invention;
(5) functionalized polyvinyl alcohol microballoon provided by the invention can be applicable to waste water detection and process field.
Brief description of the drawings
Fig. 1 functionalized polyvinyl alcohol microballoon reaction schematic diagram.
Fig. 2 is functionalized polyvinyl alcohol microballoon infrared spectrogram in embodiment 1.
Fig. 3 is functionalized polyvinyl alcohol microballoon scanning electron microscope (SEM) photograph in embodiment 2.
Fig. 4 is functionalized polyvinyl alcohol microballoon infrared spectrogram in embodiment 2.
Fig. 5 is functionalized polyvinyl alcohol microballoon infrared spectrogram in embodiment 3.
Fig. 6 is Cu (II) clearance-time plot in functionalized polyvinyl alcohol microballoon adsorbed water body in embodiment 4.
Fig. 7 is that in embodiment 4, functionalized polyvinyl alcohol microballoon detects Cu (II) UV absorption visible ray spectrogram in water body.
Fig. 8 is Cu (II) clearance-time plot in functionalized polyvinyl alcohol microballoon adsorbed water body in embodiment 5.
Fig. 9 is that in embodiment 5, functionalized polyvinyl alcohol microballoon detects Cu (II) UV absorption visible ray spectrogram in water body.
Figure 10 is Cu (II) clearance-time plot in functionalized polyvinyl alcohol microballoon adsorbed water body in embodiment 6.
Figure 11 is that in embodiment 6, functionalized polyvinyl alcohol microballoon detects Cu (II) UV absorption visible ray spectrogram in water body.
In figure, 1, epoxychloropropane and hydrochloric acid; 2, ethylenediamine, TABA (TBAB) and NaOH; 3, PAR(2-(2-pyridine) azo resorcinol) and formaldehyde.Represent polyvinyl alcohol microparticles.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples. InstituteThe method of stating is conventional method if no special instructions. Described raw material all can obtain from open commercial sources if no special instructions.
Embodiment 1
A preparation method for functionalized polyvinyl alcohol microballoon, comprises the following steps:
Inverse suspension crosslinking legal system is for polyvinyl alcohol microparticles: first by molten in 40mL water 4g polyvinyl alcohol (PVA) (1799)Separate, in boiling water bath, use mechanical agitation 1h, withdraw boiling water bath and be cooled to 60 DEG C, add 80mL atoleine and class of 1g department 80, stirThen 2h adds 2mL1molL-1Hydrochloric acid solution and the glutaraldehyde solution of 4mL, (paddle radius is rotating speed 500rpm2cm), stir after 30min, at the lower centrifugal 3min of rotating speed 4000rpm (centrifuge radius is 13.5cm), isolate microballoon, use stoneOil ether cleans 3 times, and then vacuum drying, obtains white powder solid, is polyvinyl alcohol microparticles, and particle diameter is 1-50 μ m. InsteadAnswer principle as shown in Figure 1.
Get the above-mentioned polyvinyl alcohol microparticles making of 1g and 1mL epoxychloropropane, join 30mLpH and be in 1 hydrochloric acid, waterBath is heated to 60 DEG C, continues to stir 1h under rotating speed 200rmp, and cooling rear centrifugal, centrifugal speed is 1000rpm, and the time is 1min,With distilled water cleaning 3 times, then vacuum drying 48h, uses in order to next step experiment.
Get pressed powder 1g obtained above, it is that 9 NaOH is molten that 0.01g TBAB joins 10mLpHIn liquid, pour fast 10mL ethylenediamine into, heating water bath to 60 DEG C, continues under rotating speed 200rmp to stir 4h, cooling rear centrifugal, centrifugalSpeed is 1000rpm, and the time is 1min, and with ethanol clean 3 times, vacuum drying 48h, in order to next step experiment use.
Get again product 1g obtained above, 0.1g2-(2-pyridine) azo resorcinol, 5mL formaldehyde, 5mL distilled waterAdd in there-necked flask, under rotating speed 100rmp, nitrogen continues to stir after 6h, the centrifugal 1min of centrifuge under 1000rmp, and ethanolClean 3 times, vacuum drying obtains functionalized polyvinyl alcohol microballoon.
Gained functionalized polyvinyl alcohol microballoon infrared spectrum characterization group. As shown in Figure 2, end product 1540-1650cm-1Place has had more peak, shows to have contained phenyl ring, illustrates and successfully modifies upper colour developing group.
Embodiment 2
A preparation method for functionalized polyvinyl alcohol microballoon, comprises the following steps:
First 4g polyvinyl alcohol (PVA) (1799) is dissolved in 40mL water, in boiling water bath, use mechanical agitation 1h, withdraw boiling waterBath is cooled to 60 DEG C, adds 80mL atoleine and class of 1g department 80, stirs 2h and then adds 2mL1molL-1Hydrochloric acid solutionWith the glutaraldehyde solution of 4mL, rotating speed 500rpm (paddle radius is 2cm), stirs after 30min, and at rotating speed, 4000rpm is (centrifugalMachine radius is 13.5cm) lower centrifugal 3min, isolate microballoon, with benzinum cleaning 3 times, then vacuum drying, obtains white powderPowder solid, is polyvinyl alcohol microparticles, and particle diameter is 1-50 μ m.
Get the above-mentioned polyvinyl alcohol microparticles making of 1g and 4mL epoxychloropropane, join 50mLpH and be in 2 hydrochloric acid, waterBath is heated at 80 DEG C, continues to stir after 2h under rotating speed 200rmp, and cooling rear centrifugal, centrifugal speed is 3500rpm, and the time is5min, with distilled water cleaning 3 times, then vacuum drying 48h, uses in order to next step experiment.
Get pressed powder 1g obtained above, it is 11.5 NaOH that 0.1g TBAB joins 20mLpHIn solution, pour fast 25mL ethylenediamine into, heating water bath to 80 DEG C, continues under rotating speed 500rmp to stir 6h, cooling rear centrifugal, fromHeart speed is 3500rpm, and the time is 5min, and with ethanol clean 3 times, vacuum drying 48h, in order to next step experiment use.
Get again product 1g obtained above, 1g2-(2-pyridine) azo resorcinol, 10mL formaldehyde, 10mL distilled waterAdd in there-necked flask, under rotating speed 200rmp, continue to stir after 12h, the centrifugal 5min of centrifuge under 3500rmp, ethanol cleans 3Inferior, vacuum drying obtains functionalized polyvinyl alcohol microballoon.
Gained functionalized polyvinyl alcohol microballoon scanning electron microscope observation form, infrared spectrum characterization group. As shown in Figure 3,In order to the standby microballoon spheroid form rule of top legal system, the particle diameter of this microballoon is about 1-50 μ m. As shown in Figure 4, end product exists1540—1650cm-1Place has had more peak, shows to have contained phenyl ring, illustrates and successfully modifies upper colour developing group.
Embodiment 3
A preparation method for functionalized polyvinyl alcohol microballoon, comprises the following steps:
First 4g polyvinyl alcohol (PVA) (1799) is dissolved in 40mL water, in boiling water bath, use mechanical agitation 1h, withdraw boiling waterBath is cooled to 60 DEG C, adds 80mL atoleine and class of 1g department 80, stirs 2h and then adds 2mL1molL-1Hydrochloric acid solutionWith the glutaraldehyde solution of 4mL, rotating speed 500rpm (paddle radius is 2cm), stirs after 30min, and at rotating speed, 4000rpm is (centrifugalMachine radius is 13.5cm) lower centrifugal 3min, isolate microballoon, with benzinum cleaning 3 times, then vacuum drying, obtains white powderPowder solid, is polyvinyl alcohol microparticles, and particle diameter is 1-50 μ m.
Get the above-mentioned polyvinyl alcohol microparticles making of 1g and 10mL epoxychloropropane, join 100mLpH and be in 5 hydrochloric acid,At heating water bath to 100 DEG C, continue to stir after 5h under rotating speed 2000rmp, cooling rear centrifugal, centrifugal speed is 5000rpm, the timeFor 10min, with distilled water cleaning 3 times, then vacuum drying 48h, uses in order to next step experiment.
Get pressed powder 1g obtained above, it is 13 sodium hydroxide solution that 1g TBAB joins 50mLpHIn, pour fast 50mL ethylenediamine into, heating water bath to 100 DEG C, continues under rotating speed 2000rmp to stir 10h, cooling rear centrifugal, fromHeart speed is 5000rpm, and the time is 10min, and with ethanol clean 3 times, vacuum drying 48h, in order to next step experiment use.
Get again product 1g obtained above, 2g2-(2-pyridine) azo resorcinol, 20mL formaldehyde, 20mL distilled waterAdd in there-necked flask, under rotating speed 500rmp, continue to stir after 18h, the centrifugal 10min of centrifuge under 5000rmp, ethanol cleans 3Inferior, vacuum drying obtains functionalized polyvinyl alcohol microballoon.
Gained functionalized polyvinyl alcohol microballoon infrared spectrum characterization group. As shown in Figure 5, end product 1540-1650cm-1Place has had more peak, shows to have contained phenyl ring, illustrates and successfully modifies upper colour developing group.
Embodiment 4
Polyvinyl alcohol microparticles absorption after functionalization and the application of detection copper ion:
Get 0.4gL-1Embodiment 1 prepares the functionalized polyvinyl alcohol microballoon of gained, and dropping into copper ion concentration is 100 μmol·L-1Heavy metal wastewater thereby in, after 10s, solution colour reddens. Through 6h, absorption reaches balance substantially, as shown in Figure 6, inhalesAttached removal efficiency reaches 74.9%. Scanning ultraviolet-visible spectrophotometric spectra, as shown in Figure 7, at 500-550cm-1, there is crest in place.Illustrate that this functionalized polyvinyl alcohol microballoon can detect the copper ion of removing in heavy metal wastewater thereby.
Embodiment 5
Polyvinyl alcohol microparticles absorption after functionalization and the application of detection copper ion:
Get 0.4gL-1Embodiment 2 prepares the functionalized polyvinyl alcohol microballoon of gained, and dropping into copper ion concentration is 100 μmol·L-1Heavy metal wastewater thereby in, after 10s, solution colour reddens. Through 6h, absorption reaches balance substantially, as shown in Figure 8, inhalesAttached efficiency reaches 80.9%. Scanning ultraviolet-visible spectrophotometric spectra, as shown in Figure 9, at 500-550cm-1, there is crest in place. ExplanationThis functionalized polyvinyl alcohol microballoon can detect the copper ion of removing in heavy metal wastewater thereby.
Embodiment 6
The application of the absorption of the polyvinyl alcohol microparticles after functionalization and detection copper ion:
Get 0.4gL-1Embodiment 3 prepares the functionalized polyvinyl alcohol microballoon of gained, and dropping into copper ion concentration is 100 μmol·L-1Heavy metal wastewater thereby in, after 10s, solution colour reddens. Through 6h, absorption reaches balance substantially, as shown in figure 10, inhalesAttached efficiency reaches 80.2%. Scanning ultraviolet-visible spectrophotometric spectra, as shown in 11 figure, at 500-550cm-1, there is crest in place. SayBright this functionalized polyvinyl alcohol microballoon can detect the copper ion of removing in heavy metal wastewater thereby.
The functionalized polyvinyl alcohol microballoon preparing according to above-described embodiment contains a large amount of different chelation groups, canA large amount of absorption heavy metal ions in wastewater, thus remove the heavy metal ion in waste water. By functionalized polyvinyl alcohol of the present inventionMicroballoon drops into containing in the waste water of heavy metal, can detect whether there is heavy metal ion by the change color of observing waste water, logicalOverscanning uv-vis spectra can be known the scope that heavy metal ion exists.
Claims (9)
1. a preparation method for functionalized polyvinyl alcohol microballoon, is characterized in that, comprises the steps:
1) chloro of polyvinyl alcohol microparticles: polyvinyl alcohol microparticles, epoxychloropropane, hydrochloric acid solution are mixed, and stirring in water bath is anti-Answer 1-5h, bath temperature is 60-100 DEG C, reaction finish rear centrifugal, water clean, dry, for subsequent use; Described polyvinyl alcohol microparticles,The amount ratio of epoxychloropropane, hydrochloric acid solution is 1g:1-10mL:30-100mL, and the pH value of hydrochloric acid solution is 1-5, speed of agitatorFor 200-2000rpm, centrifugal speed is 1000-5000rpm, and centrifugation time is 1-10min; The particle diameter of polyvinyl alcohol microparticles is 1-50μm；
2) amination of polyvinyl alcohol microparticles: by the chloro polyvinyl alcohol microparticles of step 1) gained and TBAB, secondDiamines, sodium hydroxide solution mix, stirring in water bath reaction 4-10h, and bath temperature is 60-100 DEG C, reaction finishes rear centrifugal, useEthanol cleaning, drying, for subsequent use;
3) by step 2) amination polyvinyl alcohol microparticles and the 2-(2-pyridine of gained) azo resorcinol, formaldehyde, distilled water be mixedEven, under nitrogen, stir 6-18h, centrifugal after reaction, clean the dry end product that to obtain with ethanol.
2. the preparation method of functionalized polyvinyl alcohol microballoon according to claim 1, is characterized in that: the water-bath of step 1)Temperature is 80 DEG C, and speed of agitator is 500rpm, and the stirring reaction time is 2h, and centrifugation time is 5min, and centrifugal speed is3500rpm。
3. the preparation method of functionalized polyvinyl alcohol microballoon according to claim 1, is characterized in that: poly-described in step 1)The amount ratio of vinyl alcohol microballoon, epoxychloropropane, hydrochloric acid solution is 1g:4mL:50mL, and the pH of hydrochloric acid solution is 2.
4. the preparation method of functionalized polyvinyl alcohol microballoon according to claim 1, is characterized in that: step 2) describedThe amount ratio of chloro polyvinyl alcohol microparticles, TBAB, ethylenediamine, sodium hydroxide solution is 1g:0.01-1g:10-50mL:10-50mL, the pH of sodium hydroxide solution is 9-13, and speed of agitator is 200-2000rpm, and centrifugal speed is 1000-5000rpm, centrifugation time is 1-10min.
5. according to the preparation method of the functionalized polyvinyl alcohol microballoon described in claim 1 or 4, it is characterized in that: step 2) instituteState bath temperature be 80 DEG C, speed of agitator is 500rpm, the stirring reaction time is 6h, centrifugation time is 5min, centrifugal speedDegree is 3500rpm.
6. according to the preparation method of the functionalized polyvinyl alcohol microballoon described in claim 1 or 4, it is characterized in that: step 2) instituteThe amount ratio of the chloro polyvinyl alcohol microparticles stated, TBAB, ethylenediamine, sodium hydroxide solution is 1g:0.1g:20mL:20mL, described sodium hydroxide solution pH is 11.5.
7. the preparation method of functionalized polyvinyl alcohol microballoon according to claim 1, is characterized in that: described in step 3)Amination polyvinyl alcohol microparticles, 2-(2-pyridine) amount ratio of azo resorcinol, formaldehyde, distilled water is 1g:0.1-2g:5-20mL:5-20mL, speed of agitator is 100-500rpm, and centrifugal speed is 1000-5000rpm, and the time is 1-10min.
8. according to the preparation method of the functionalized polyvinyl alcohol microballoon described in claim 1 or 7, it is characterized in that: step 3) is stirredMix hybrid reaction 12h, speed of agitator is 200rpm, and centrifugation time is 5min, and centrifugal speed is 3500rpm.
9. the application of functionalized polyvinyl alcohol microballoon claimed in claim 1 in heavy metal wastewater thereby detects and processes.
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| CN104743681B (en) * | 2015-04-13 | 2017-03-01 | 西安石油大学 | The preparation method and application of sewage purification medium |
| CN104874369B (en) * | 2015-05-11 | 2017-03-29 | 河海大学 | Modified polyvinyl alcohol microparticles of a kind of coloring functionization and preparation method and application |
| CN105129876B (en) * | 2015-08-11 | 2018-05-22 | 厦门建霖健康家居股份有限公司 | A kind of sustained release VC gels |
| CN105784700A (en) * | 2016-05-06 | 2016-07-20 | 河海大学 | Preparation method and application of chemical sensor for chromogenic detection on heavy metals |
| CN106587443A (en) * | 2017-01-23 | 2017-04-26 | 福建海西滤水龙头研究中心有限公司 | Garbage percolate filtering device for garbage transfer station |
| CN107442078B (en) * | 2017-03-16 | 2020-09-29 | 浙江工商大学 | Preparation and application of color-changing fiber AMTF-PAR |
| CN107233867B (en) * | 2017-03-16 | 2020-11-03 | 浙江工商大学 | Preparation and application of color-changing fiber AHTF-PAR |
| CN107233868B (en) * | 2017-03-16 | 2020-11-03 | 浙江工商大学 | Preparation and application of color-changing fiber IAHF-PAR |
| CN107233866B (en) * | 2017-03-16 | 2020-11-03 | 浙江工商大学 | Preparation and application of color-changing fiber AMF-PAR |
| CN107558208B (en) * | 2017-03-16 | 2020-11-03 | 浙江工商大学 | Preparation and application of color-changing fiber APF-PAR |
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| CN101298040B (en) * | 2008-06-19 | 2011-12-07 | 同济大学 | Mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbing agent and preparation thereof |
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