CN103788308A - Method for preparing macromolecular imprinting adsorbent by polymerization of Pickering emulsion - Google Patents
Method for preparing macromolecular imprinting adsorbent by polymerization of Pickering emulsion Download PDFInfo
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Abstract
The invention relates to a method for preparing a macromolecular imprinting adsorbent by the polymerization of Pickering emulsion, and belongs to the technical field of preparation of environmental functional materials. The method comprises the following steps of synthesizing silicon dioxide particles by an improved stober method, and modifying the silicon dioxide particles to enhance the hydrophobicity of the silicon dioxide particles by using oleic acid; stabilizing water-in-oil type high-internal phase Pickering emulsion added with template molecules by using the modified silicon dioxide particles and a certain amount of surfactant Hypermer2296, performing polymerization at certain temperature, and performing a series of treatment to obtain the adsorbent, wherein the adsorbent is applied to the selective adsorption and separation of high-performance cyhalothrin. The prepared adsorbent has the advantages of open pore structure, connecting pores, high thermal stability, high mechanical strength, proper hydrophobicity and the like, and the forms of the pores can be controlled to improve the template molecule adsorption capacity by changing parameters of the emulsion; the adsorbent has high adsorption capability and selective adsorption for the high-performance cyhalothrin.
Description
Technical field
The present invention relates to a kind of Pickering letex polymerization and prepare the method for macropore trace sorbent material, belong to environment functional material preparing technical field.
Background technology
In several years of past, numerous areas is paid close attention to and be applied to large pore material widely because of its significant anti-pressure ability, for example catalyzer, organizational project, absorption and separate etc.The traditional method of preparing this large pore material is exactly to carry out stable High Internal Phase Emulsion by formation with tensio-active agent to produce, and this emulsion deficient in stability, and the mechanical property of the large pore material of preparation is poor, and macropore and connecting pore are also quite little.In recent years, a kind of method of only carrying out stable emulsion by solid particulate without tensio-active agent had obtained general application, and this emulsion is called as Pickering emulsion.The emulsion that this method forms and traditional relatively have better stability of emulsion and rigidity, thereby a kind of technology of Pickering High Internal Phase Emulsion by name has been born.The material of being prepared by this method has the advantages such as macropore, connecting pore and good mechanical property.
Molecular imprinting is that preparation has the three-dimensional cross-linked high molecular technology of predetermined recognition function binding site, and the molecularly imprinted polymer (MIPs) of preparation can produce specific adsorption to template molecule.Surface molecule print technology is by being based upon molecular recognition site on the surface of substrate material, preferably resolve some major defects that traditional molecular imprinting entirety also exists, as excessively dark in avtive spot embedding, the kinetic rate of mass transfer and charge transfer is slow, and the dynamic performance of adsorption-desorption is not good etc.
Lambda-cyhalothrin (CL) is often used to sterilant, with fenvalerate (FN), the same pyrethroid that belongs to of bifenthrin.Due to its polluted water and can bring injury to human body, for this reason, in detection and processing environment water body, lambda-cyhalothrin is necessary in time, but complicated component in environment water, selectivity identification seems particularly important with separate targets pollutent (lambda-cyhalothrin).
Summary of the invention
The present invention is hydrolyzed alkyl silicate by the St ber method of improvement and the method for condensing in alcohol is carried out synthetic silica particle, and the method that uses oleic acid to soak is carried out modification to it and obtained hydrophobic silicon dioxide granule.Take the silicon dioxide granule of the oleic acid modification that makes as stable particle, in water, be Calcium dichloride dihydrate (CaCl subsequently
22H
2o) the aqueous solution, oil phase is vinylbenzene (St), polyoxyethylene glycol two (methacrylic acid) ester (PEGDMA), Vinylstyrene (DVB), acrylamide (AM), lambda-cyhalothrin (CL) and 2,2'-Diisopropyl azodicarboxylate (AIBN), form stable Pickering High Internal Phase Emulsion, obtain porous by radical polymerization and there is the sorbent material that specificity is selected, be molecularly imprinted polymer (MIPFs), and the selective adsorption that sorbent material is applied to the lambda-cyhalothrin (CL) in the aqueous solution with separate.
The technical solution used in the present invention is:
(1) preparation of silicon dioxide granule:
In round-bottomed flask, add ethanol, add solution of ammonium hydroxide and deionized water under magnetic agitation, stir after 0.5-1.5h, add tetraethyl orthosilicate (TEOS), mixture stirs 10 ~ 14h under the speed of 600 ~ 800rpm; By whizzer, mixture is separated, and with ethanol to its rinse at least three times, then vacuum-drying, obtains silicon dioxide granule.
(2) preparation of the silicon dioxide granule of oleic acid modification:
Silicon dioxide granule is immersed in the mixed solution of chloroform and oleic acid, stir 2 ~ 4h, then make its precipitation collect the silicon dioxide granule of oleic acid modification by methyl alcohol, and use chloroform and methyl alcohol respectively they to be repeated to soak and are precipitated and remove excessive oleic acid, finally at 100 ~ 140 ℃, be dried, obtain the silicon dioxide granule of oleic acid modification.
(3) preparation of the sorbent material with porous and specificity selection obtaining by the polymerization of Pickering High Internal Phase Emulsion:
The first step, the preparation of water-in-oil-type (w/o type) Pickering High Internal Phase Emulsion:
Under mechanical stirring, by vinylbenzene (St), polyoxyethylene glycol two (methacrylic acid) ester (PEGDMA), Vinylstyrene (DVB), acrylamide (AM), lambda-cyhalothrin (CL) and 2,2'-Diisopropyl azodicarboxylate (AIBN) add in round-bottomed flask successively, and the mixed solution in the backward bottle of 30min leads to nitrogen and allows in the dark acrylamide (AM) and lambda-cyhalothrin (CL) self-assembly 10 ~ 14h; Stir and add the silicon dioxide granule of oleic acid modification to obtain oil phase to mixed solution with 900 ~ 1100rpm, stir after 15min, continue to stir with 300 ~ 500rpm, in 5min, in oil phase, dropwise add the U-Ramin MC aqueous solution, subsequently, in 2min, add wherein tensio-active agent Hypermer 2296 to stablize Pickering emulsion, the Pickering High Internal Phase Emulsion of this w/o type will be placed on and in ice bath, continue to be down to room temperature and prevent from raising owing to continuing to stir the temperature causing.
Second step, the preparation of MIPFs:
The Pickering High Internal Phase Emulsion of the w/o type of formation is transferred in centrifuge tube, and at 60 ~ 80 ℃, polymerization 22 ~ 26h obtains product MIPFs, afterwards vacuum-drying 22 ~ 26h at 100 ~ 140 ℃; And then use apparatus,Soxhlet's to wash purifying to product, last, at 100 ~ 140 ℃, make the MIPFs of purifying be dried 22 ~ 26h.
Wherein the massfraction of the solution of ammonium hydroxide solution described in step (1) is 25%; The volume ratio of described ethanol, solution of ammonium hydroxide, water and tetraethyl orthosilicate is: 80 ~ 100:3.0 ~ 4.0:9 ~ 11:5.0 ~ 7.0.
Wherein the ratio of the mixed solution of the silicon dioxide granule described in step (2) and chloroform and oleic acid is: 0.8 ~ 1.2g: 15mL, wherein in mixed solution, chloroform and oleic acid mol ratio are 1:1 ~ 3.
Wherein the volume ratio of the vinylbenzene described in the first step of step (3), polyoxyethylene glycol two (methacrylic acid) ester and Vinylstyrene is 5.5 ~ 9.5:5.5 ~ 6.5:1.0 ~ 2.0, described acrylamide, lambda-cyhalothrin and 2, the mol ratio of 2'-Diisopropyl azodicarboxylate is 1.5 ~ 2.5:0.3 ~ 0.7:0.05 ~ 0.15, and wherein the ratio of vinylbenzene and acrylamide is 5.5 ~ 9.5 mL:1.5 ~ 2.5mmol; The described silicon dioxide granule adding and cinnamic ratio are 0.7 ~ 0.8 g:5.5 ~ 9.5mL; The described U-Ramin MC aqueous solution adding and cinnamic volume ratio are 20 ~ 40:5.5 ~ 9.5, and wherein the concentration of the U-Ramin MC aqueous solution is 0.25 ~ 0.30mol/L; The described tensio-active agent Hypermer adding 2296 is 0.5 ~ 1.25 g:5.5 ~ 9.5 with cinnamic ratio.
Wherein the washing purifying described in the second step of step (3) is for first washing MIPFs with deionized water, and then with acetone, its washing is removed to remaining tensio-active agent, with the mixed solution of methyl alcohol and Glacial acetic acid, MIPFs is washed and removes CL template molecule again, repeated washing, until can't detect template molecule in elutriant; Wherein said methyl alcohol and the volume ratio of Glacial acetic acid are 95:5.
Method and the trace sorbent material (MIPFs) of preparing non-trace sorbent material (NIPFs) are similar, and the consumption of the consumption of agents useful for same during with reference to MIPFs corresponding to preparation adds, and just do not add CL.
Technological merit of the present invention: this product, in conjunction with Pickering High Internal Phase Emulsion and molecular imprinting, has both length concurrently, has macropore and connecting pore and lambda-cyhalothrin (CL) is had to the feature of specific adsorption.In experiment, use solids (SPs) and nonionogenic tenside (Hypermer 2296) to carry out jointly stabilizing emulsion, stability of emulsion is improved greatly, and strengthened the mechanical property of sorbent material.
Accompanying drawing explanation
Fig. 1 is some illustrations in Pickering High Internal Phase Emulsion forming process, (a) phase-separated system; (b) the Pickering High Internal Phase Emulsion of the w/o type that interior phase volume fraction is 72.9%; (c) polymer chips; (d) Photomicrograph of the Pickering High Internal Phase Emulsion of w/o type; (e) closeup photograph on polymer chips surface.
Fig. 2 is the light micrograph that carrys out the Pickering High Internal Phase Emulsion of stable W/O by the tensio-active agent of solid particulate and different amounts.
Fig. 3 is the scanning electron microscope (SEM) photograph of MIPFs, is respectively (a) MIPFs not soaking with HF and MIPFs (b) soaking with HF.
Fig. 4 is the analysis (b) of infrared spectrum (a) and the principal element of MIPFs.
Fig. 5 is the thermogravimetric spectrogram of MIPFs and NIPFs.
Fig. 6 is MIPFs and the NIPFs contact angle with respect to water.
Fig. 7 is HIPEs figure of (b) in (a) and toluene in water.
Embodiment
In the specific embodiment of the invention, recognition performance evaluation is carried out by the following method: utilize Staticadsorption experiment to complete.Certain density 10ml lambda-cyhalothrin (CL) solution is joined in the centrifuge tube of 10mL, add a certain amount of trace sorbent material, be placed on 25
oin C constant temperature waters, leave standstill some hours, after absorption, lambda-cyhalothrin content is measured with ultraviolet-visible pectrophotometer, and calculates loading capacity according to result; Select several structures and kin chrysanthemum ester compound, such as fenvalerate, diethyl phthalate etc., as competitive adsorption thing, participate in the recognition performance of research MIPFs.
Below in conjunction with concrete embodiment, the present invention will be further described.
Embodiment 1:
(1) preparation of silicon dioxide granule:
In the round-bottomed flask of 250mL, add the ethanol of 80mL, under magnetic agitation, adding 3.0mL massfraction is 25% solution of ammonium hydroxide and 9mL water, stir after 0.5h, add 5.0mL tetraethyl orthosilicate (TEOS), mixture stirs 10h under the speed of 600rpm.By whizzer, mixture is separated, and with ethanol to its rinse at least three times, then vacuum-drying.
(2) preparation of the silicon dioxide granule of oleic acid modification:
It is in the chloroform of 1:1 and the mixed solution of oleic acid that 0.8g silicon dioxide granule is immersed in to 15mL mol ratio, stir 2h, then make its precipitation collect the silicon dioxide granule of oleic acid modification by methyl alcohol, and use chloroform and methyl alcohol respectively they to be repeated to soak and are precipitated and remove excessive oleic acid, finally dry at 100 ℃.
(3) preparation of the sorbent material with porous and specificity selection obtaining by the polymerization of Pickering High Internal Phase Emulsion:
1) preparation of w/o type Pickering High Internal Phase Emulsion
Under mechanical stirring, by 5.5mL vinylbenzene (St), 5.5mL polyoxyethylene glycol two (methacrylic acid) ester (PEGDMA), 1.0mL Vinylstyrene (DVB), 1.5mmol acrylamide (AM), 0.3mmol lambda-cyhalothrin (CL) and 0.05mmol2,2'-Diisopropyl azodicarboxylate (AIBN) successively adds in the round-bottomed flask of 100mL, in the mixed solution in the backward bottle of 30min, leads to nitrogen and allows in the dark acrylamide (AM) and lambda-cyhalothrin (CL) self-assembly 10h.Stir and add the silicon dioxide granule of 0.7g oleic acid modification to obtain oil phase in mixed solution with 900rpm.Stir after 15min, continue to stir with 300rpm, in 5min, to the U-Ramin MC aqueous solution that dropwise adds 20mL0.25mol/L in oil phase, subsequently, in 2min, add wherein 0.5g tensio-active agent Hypermer 2296 to stablize Pickering emulsion.The Pickering High Internal Phase Emulsion of this w/o type will be placed on and in ice bath, continue to be down to room temperature and prevent from raising owing to continuing to stir the temperature causing.
2) preparation of MIPFs
The Pickering High Internal Phase Emulsion of the w/o type of formation is transferred in centrifuge tube, and at 60 ℃, polymerization 22h obtains product MIPFs, afterwards vacuum-drying 22h at 100 ℃.And then use apparatus,Soxhlet's to wash purifying to product, first with 40mL deionized water, MIPFs is washed to 5h, and then with 20mL acetone, its washing 10h is removed to remaining tensio-active agent.Use again the mixed solution (95:5, V/V) of 40mL methyl alcohol and Glacial acetic acid to remove CL template molecule to MIPFs washing 2h, repeat 6 times, until can't detect template molecule in elutriant.Finally, at 100 ℃, make the dry 22h of MIPFs of purifying.Method and the trace sorbent material (MIPFs) of preparing non-trace sorbent material (NIPFs) are similar, and the consumption of the consumption of agents useful for same during with reference to MIPFs corresponding to preparation adds, and just do not add CL.
Embodiment 2:
(1) preparation of silicon dioxide granule:
In the round-bottomed flask of 250mL, add the ethanol of 90mL, under magnetic agitation, adding 3.14mL massfraction is 25% solution of ammonium hydroxide and 10mL water, stir after 1h, add 6mL tetraethyl orthosilicate (TEOS), mixture stirs 12h under the speed of 700rpm.By whizzer, mixture is separated, and with ethanol to its rinse at least three times, then vacuum-drying.
(2) preparation of the silicon dioxide granule of oleic acid modification:
It is in the chloroform of 1:2 and the mixed solution of oleic acid that 1g silicon dioxide granule is immersed in to 15mL mol ratio, stir 3h, then make its precipitation collect the silicon dioxide granule of oleic acid modification by methyl alcohol, and use chloroform and methyl alcohol respectively they to be repeated to soak and are precipitated and remove excessive oleic acid, finally dry at 120 ℃.
(3) preparation of the sorbent material with porous and specificity selection obtaining by the polymerization of Pickering High Internal Phase Emulsion:
1) preparation of w/o type Pickering High Internal Phase Emulsion
Under mechanical stirring, by 7.5mL vinylbenzene (St), 6mL polyoxyethylene glycol two (methacrylic acid) ester (PEGDMA), 1.5mL Vinylstyrene (DVB), 2.0mmol acrylamide (AM), 0.5mmol lambda-cyhalothrin (CL) and 0.1mmol2,2'-Diisopropyl azodicarboxylate (AIBN) successively joins in the round-bottomed flask of 100mL, in the backward bottle of 30min, in mixed solution, leads to nitrogen and allows in the dark acrylamide (AM) and lambda-cyhalothrin (CL) self-assembly 12h.Stir and add the silicon dioxide granule of 0.75g oleic acid modification to obtain oil phase in mixed solution with 1000rpm.Stir after 15min, continue to stir with 400rpm, in 5min, to the U-Ramin MC aqueous solution that dropwise adds 35mL0.27mol/L in oil phase, subsequently, in 2min, add wherein 0.75g tensio-active agent Hypermer 2296 to stablize Pickering emulsion.The Pickering High Internal Phase Emulsion of this w/o type will be placed on and in ice bath, continue to be down to room temperature and prevent from raising owing to continuing to stir the temperature causing.
2) preparation of MIPFs
The Pickering High Internal Phase Emulsion of the w/o type of formation is transferred in centrifuge tube, and at 70 ℃, polymerization 24h obtains product MIPFs, afterwards vacuum-drying 24h at 120 ℃.And then use apparatus,Soxhlet's to wash purifying to product, first with 50mL deionized water, MIPFs is washed to 6h, and then with 30mL acetone, its washing 12h is removed to remaining tensio-active agent.Use again the mixed solution (95:5, V/V) of 50mL methyl alcohol and Glacial acetic acid to remove CL template molecule to MIPFs washing 3h, repeat 6 times, until can't detect template molecule in elutriant.Finally, at 120 ℃, make the dry 24h of MIPFs of purifying.Method and the trace sorbent material (MIPFs) of preparing non-trace sorbent material (NIPFs) are similar, and the consumption of the consumption of agents useful for same during with reference to MIPFs corresponding to preparation adds, and just do not add CL.
Fig. 1 is some illustrations in Pickering High Internal Phase Emulsion forming process in embodiment 2.(a) closeup photograph on Photomicrograph (e) the polymer chips surface of the Pickering High Internal Phase Emulsion of Pickering High Internal Phase Emulsion (c) polymer chips (d) w/o type of the w/o type that the interior phase volume fraction of phase-separated system (b) is 72.9%
Fig. 3 is the scanning electron microscope (SEM) photograph of the MIPFs in embodiment 2, is respectively (a) MIPFs not soaking with HF and MIPFs (b) soaking with HF.
Fig. 4 is the analysis (b) of infrared spectrum (a) and the principal element of the MIPFs in embodiment 2,1110 cm
-1, 954 cm
-1and 787 cm
-1the absorption peak at place proves the existence of solid particulate SPs; 1491 cm
-1, 3070 cm
-1and 3030 cm
-1the absorption peak at place proves that monomer St participates in polymerization; 1725 cm
-1the absorption peak at place and 0.8461% N content prove that AM participates in polymerization; 60.76% C content proves to successfully synthesize MIPFs.
Fig. 5 is MIPFs in embodiment 2 and the thermogravimetric spectrogram of NIPFs, and both thermogravimetric spectrogram trend is quite approaching, has good thermostability at 250 ℃, shows that both morphological structures and size distribution are similar.
Fig. 6 is MIPFs in embodiment 2 and the NIPFs contact angle with respect to water, and the contact angle of MIPFs and NIPFs is respectively 125 ° and 122 °.
Fig. 7 is HIPEs figure of (b) in (a) and toluene in water in embodiment 2, and demonstrating HIPEs is the emulsion of w/o type.
Embodiment 3:
(1) preparation of silicon dioxide granule:
In the round-bottomed flask of 250mL, add the ethanol of 100mL, under magnetic agitation, adding 4.0mL massfraction is 25% solution of ammonium hydroxide and 11mL water, stir after 1.5h, add 7.0mL tetraethyl orthosilicate (TEOS), mixture stirs 14h under the speed of 800rpm.By whizzer, mixture is separated, and with ethanol to its rinse at least three times, then vacuum-drying.
(2) preparation of the silicon dioxide granule of oleic acid modification:
It is in the chloroform of 1:3 and the mixed solution of oleic acid that 1.2g silicon dioxide granule is immersed in to 15mL mol ratio, stir 4h, then make its precipitation collect the silicon dioxide granule of oleic acid modification by methyl alcohol, and use chloroform and methyl alcohol respectively they to be repeated to soak and are precipitated and remove excessive oleic acid, finally dry at 140 ℃.
(3) preparation of the sorbent material with porous and specificity selection obtaining by the polymerization of Pickering High Internal Phase Emulsion:
1) preparation of w/o type Pickering High Internal Phase Emulsion
Under mechanical stirring, by 9.5mL vinylbenzene (St), 6.5mL polyoxyethylene glycol two (methacrylic acid) ester (PEGDMA), 2.0mL Vinylstyrene (DVB), 2.5mmol acrylamide (AM), 0.7mmol lambda-cyhalothrin (CL) and 0.2mmol2,2'-Diisopropyl azodicarboxylate (AIBN) successively joins in the round-bottomed flask of 100mL, in the mixed solution in the backward bottle of 30min, leads to nitrogen and allows in the dark acrylamide (AM) and lambda-cyhalothrin (CL) self-assembly 14h.Stir and add the silicon dioxide granule of 0.8g oleic acid modification to obtain oil phase in mixed solution with 1100rpm.Stir after 15min, continue to stir with 500rpm, in 5min, to the U-Ramin MC aqueous solution that dropwise adds 40mL0.30mol/L in oil phase, subsequently, in 2min, add wherein 1.25g tensio-active agent Hypermer 2296 to stablize Pickering emulsion.The Pickering High Internal Phase Emulsion of this w/o type will be placed on and in ice bath, continue to be down to room temperature and prevent from raising owing to continuing to stir the temperature causing.
2) preparation of MIPFs
The Pickering High Internal Phase Emulsion of the w/o type of formation is transferred in centrifuge tube, and at 80 ℃, polymerization 26h obtains product MIPFs, afterwards vacuum-drying 26h at 140 ℃.And then use apparatus,Soxhlet's to wash purifying to product, first with 60mL deionized water, MIPFs is washed to 7h, and then with 40mL acetone, its washing 14h is removed to remaining tensio-active agent.Use again the mixed solution (95:5, V/V) of 60mL methyl alcohol and Glacial acetic acid to remove CL template molecule to MIPFs washing 4h, repeat 6 times, until can't detect template molecule in elutriant.Finally, at 140 ℃, make the dry 26h of MIPFs of purifying.Method and the trace sorbent material (MIPFs) of preparing non-trace sorbent material (NIPFs) are similar, and the consumption of the consumption of agents useful for same during with reference to MIPFs corresponding to preparation adds, and just do not add CL.
Fig. 2 is the light micrograph that carrys out the Pickering High Internal Phase Emulsion of stable W/O by the tensio-active agent of solid particulate and different amounts.Along with the increase gradually of dosage of surfactant, drop size diminishes gradually and deformation extent strengthens, and the contact surface of adjacent drops increases, and stability of emulsion increases, and that a main stabilization is solid particulate SPs.
Below in conjunction with concrete embodiment, the present invention will be further described:
Test example 1:
Get 10ml starting point concentration and be respectively 10 mg/L, 30 mg/L, 50 mg/L, 80 mg/L, 100 mg/L, 150 mg/L, 200 mg/L, lambda-cyhalothrin (CL) solution of 250mg/L (using ethanol and dual distilled water by volume the mixed solution of 1:1 prepare as solvent) join in centrifuge tube, regulating pH value with dilute hydrochloric acid or weak ammonia is 6.0, add respectively trace sorbent material and the non-trace sorbent material of preparation in 10mg embodiment 2, test fluid is placed in the water bath chader of 25 ℃ after 12h, by centrifugal, trace sorbent material and non-trace sorbent material and solution separating are opened, the micropore nitrocellulose filter that re-uses aperture and be 0.45mm filters and removes the particle suspending solution.CL concentration in filtrate is calculated mensuration under the wavelength of 278nm by ultraviolet spectrophotometer, and calculates loading capacity and process according to result.Result shows, two kinds of absorption behaviors belong to monolayer adsorption, and the maximum monolayer adsorption capacity of MIPFs and NIPFs is respectively 46.10 umol g
-1with 25.42 umol g
-1, also proved that MIPFs has the more binding site similar to microsphere than NIPFs.
Test example 2:
Getting the lambda-cyhalothrin that 10mL starting point concentration is 100mg/L (CL) solution joins in centrifuge tube, regulating pH value with dilute hydrochloric acid or weak ammonia is 6.0, add respectively trace sorbent material and non-trace sorbent material, test fluid is placed in the water bath chader of 25 ℃, in 0.5h, 2h, 4h, 6h, 8h, 12h, takes out respectively.By centrifugal, trace sorbent material and non-trace sorbent material and solution separating are opened, the micropore nitrocellulose filter that re-uses aperture and be 0.45mm filters and removes the particle suspending solution.CL concentration in filtrate is calculated mensuration under the wavelength of 278nm by ultraviolet spectrophotometer, and calculates loading capacity according to result.Result shows, the adsorption process of MIPFs can be divided into quick stage (front 4h) and slow stage, and NIPFs synchronously increases slightly.MIPFs reaches 73.45% of balancing capacity in the loading capacity in quick stage, slowly increase until balance afterwards, prove the impact of microsphere binding site on absorption, and this absorption behavior belongs to monolayer adsorption, in addition, microsphere has larger adsorption equilibrium capacity and adsorption rate than non-microsphere.
Test example 3:
Select the ester compound that fenvalerate (FN), diethyl phthalate (DEP) they are competitive adsorption, the solution of the above two kinds of ester compounds of preparation respectively, and concentration is 100mg/L.Getting respectively 10mL joins in centrifuge tube, regulating pH value with dilute hydrochloric acid or weak ammonia is 6.0, add respectively trace sorbent material and the non-trace sorbent material of preparation in 10mg embodiment 2, test fluid is placed in the water bath chader of 25 ℃ after 12h, by centrifugal, trace sorbent material and non-trace sorbent material and solution separating are opened, the micropore nitrocellulose filter that re-uses aperture and be 0.45mm filters and removes the particle suspending solution.CL, FN in filtrate, the concentration of DEP solution respectively by ultraviolet spectrophotometer at 278 nm, under the wavelength of 277.5 nm and 275 nm, calculate and measure, and calculate loading capacity according to result.Result shows, MIPFs and NIPFs are efficient CL>FN>DEP for the maximum adsorption capacity of three kinds of esters from big to small; For the maximum adsorption capacity of CL, FN, DEP, MIPFs is than NIPFs many 7.88 umol g respectively
-1, 1.69 umol g
-1, 1.065 umol g
-1.Illustrate that MIPFs has specific adsorption for CL with respect to FN and DEP, there is single-minded selectivity.
Claims (6)
1. a method for macropore trace sorbent material is prepared in Pickering letex polymerization, it is characterized in that, prepares according to following step:
(1) preparation of silicon dioxide granule:
In round-bottomed flask, add ethanol, add solution of ammonium hydroxide and deionized water under magnetic agitation, stir after 0.5-1.5h, add tetraethyl orthosilicate, mixture stirs 10 ~ 14h under the speed of 600 ~ 800rpm; By whizzer, mixture is separated, and with ethanol to its rinse at least three times, then vacuum-drying, obtains silicon dioxide granule;
(2) preparation of the silicon dioxide granule of oleic acid modification:
Silicon dioxide granule is immersed in the mixed solution of chloroform and oleic acid, stir 2 ~ 4h, then make its precipitation collect the silicon dioxide granule of oleic acid modification by methyl alcohol, and use chloroform and methyl alcohol respectively they to be repeated to soak and are precipitated and remove excessive oleic acid, finally at 100 ~ 140 ℃, be dried, obtain the silicon dioxide granule of oleic acid modification;
(3) preparation of the sorbent material with porous and specificity selection obtaining by the polymerization of Pickering High Internal Phase Emulsion:
The first step, the preparation of w/o type Pickering High Internal Phase Emulsion:
Under mechanical stirring, by vinylbenzene, polyoxyethylene glycol two (methacrylic acid) ester, Vinylstyrene, acrylamide, lambda-cyhalothrin and 2,2'-Diisopropyl azodicarboxylate add in round-bottomed flask successively, and the mixed solution in the backward bottle of 30min leads to nitrogen and allows in the dark acrylamide and lambda-cyhalothrin self-assembly 10 ~ 14h; Stir and add the silicon dioxide granule of oleic acid modification to obtain oil phase to mixed solution with 900 ~ 1100rpm, stir after 15min, continue to stir with 300 ~ 500rpm, in 5min, in oil phase, dropwise add the U-Ramin MC aqueous solution, subsequently, in 2min, add wherein tensio-active agent Hypermer 2296 to stablize Pickering emulsion, the Pickering High Internal Phase Emulsion of this w/o type will be placed on and in ice bath, continue to be down to room temperature and prevent from raising owing to continuing to stir the temperature causing;
Second step, the preparation of MIPFs:
The Pickering High Internal Phase Emulsion of the w/o type of formation is transferred in centrifuge tube, and at 60 ~ 80 ℃, polymerization 22 ~ 26h obtains product MIPFs, afterwards vacuum-drying 22 ~ 26h at 100 ~ 140 ℃; And then use apparatus,Soxhlet's to wash purifying to product, last, at 100 ~ 140 ℃, make the MIPFs of purifying be dried 22 ~ 26h.
2. the method for macropore trace sorbent material is prepared in a kind of Pickering letex polymerization according to claim 1, it is characterized in that, the massfraction of the solution of ammonium hydroxide solution described in step (1) is 25%; The volume ratio of described ethanol, solution of ammonium hydroxide, water and tetraethyl orthosilicate is: 80 ~ 100:3.0 ~ 4.0:9 ~ 11:5.0 ~ 7.0.
3. the method for macropore trace sorbent material is prepared in a kind of Pickering letex polymerization according to claim 1, it is characterized in that, the ratio of the mixed solution of the silicon dioxide granule described in step (2) and chloroform and oleic acid is: 0.8 ~ 1.2g: 15mL, wherein in mixed solution, chloroform and oleic acid mol ratio are 1:1 ~ 3.
4. the method for macropore trace sorbent material is prepared in a kind of Pickering letex polymerization according to claim 1, it is characterized in that, the volume ratio of the vinylbenzene described in the first step of step (3), polyoxyethylene glycol two (methacrylic acid) ester and Vinylstyrene is 5.5 ~ 9.5:5.5 ~ 6.5:1.0 ~ 2.0, described acrylamide, lambda-cyhalothrin and 2, the mol ratio of 2'-Diisopropyl azodicarboxylate is 1.5 ~ 2.5:0.3 ~ 0.7:0.05 ~ 0.15, and wherein the ratio of vinylbenzene and acrylamide is 5.5 ~ 9.5 mL:1.5 ~ 2.5mmol; The described silicon dioxide granule adding and cinnamic ratio are 0.7 ~ 0.8 g:5.5 ~ 9.5mL; The described U-Ramin MC aqueous solution adding and cinnamic volume ratio are 20 ~ 40:5.5 ~ 9.5, and wherein the concentration of the U-Ramin MC aqueous solution is 0.25 ~ 0.30mol/L; The described tensio-active agent Hypermer adding 2296 is 0.5 ~ 1.25 g:5.5 ~ 9.5 with cinnamic ratio.
5. the method for macropore trace sorbent material is prepared in a kind of Pickering letex polymerization according to claim 1, it is characterized in that, washing purifying described in the second step of step (3) is for first washing MIPFs with deionized water, and then with acetone, its washing is removed to remaining tensio-active agent, with the mixed solution of methyl alcohol and Glacial acetic acid, MIPFs is washed and removes CL template molecule again, repeated washing, until can't detect template molecule in elutriant; Wherein said methyl alcohol and the volume ratio of Glacial acetic acid are 95:5.
6. the method for macropore trace sorbent material is prepared in a kind of Pickering letex polymerization according to claim 1, it is characterized in that, the selective adsorption that prepared macropore trace sorbent material is applied to the lambda-cyhalothrin in the aqueous solution with separate.
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