CN104086795A - Magnetic molecularly imprinted polymer as well as preparation and application thereof - Google Patents
Magnetic molecularly imprinted polymer as well as preparation and application thereof Download PDFInfo
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- CN104086795A CN104086795A CN201410329140.3A CN201410329140A CN104086795A CN 104086795 A CN104086795 A CN 104086795A CN 201410329140 A CN201410329140 A CN 201410329140A CN 104086795 A CN104086795 A CN 104086795A
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- magnetic
- nonyl phenol
- polybenzimidazole
- molecularly imprinted
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Abstract
The invention discloses a magnetic molecularly imprinted polymer as well as a preparation and an application thereof. Fe3O4 microspheres are taken as magnetic nanoparticles; nonyl phenol is taken as a template molecule; soluble polybenzimidazole (OPBI) is taken as a functional monomer; N,N-dimethylacetamide is taken as a solvent, thereby preparing a magnetic molecularly imprinted material (MMIP). The MMIP is taken as an adsorbent, and the nonyl phenol in water is efficiently adsorbed. The used magnetic molecularly imprinted material is significantly better than the traditional enrichment material, has a simple preparation method, excellent selection property, and significant treatment effect, and has good economic and environmental benefits when being used for removing the nonyl phenol in environmental water.
Description
Technical field
The present invention relates to a kind of beneficiation technologies of field of Environment Protection, is specifically related to a kind of magnetic molecularly imprinted polymer and preparation method, utilizes magnetic molecularly imprinted material as sorbent material, the nonyl phenol in enrichment environmental water body simultaneously.
Background technology
Nonyl phenol (NP) is a kind of common environment incretion interferent (EDCs), and the content in environment is extremely low.There is the structure or the function that are similar to hormone, disturb the normal physiological function of organism, cause reproductive function decline, sexual prematurity, feminize and carninomatosis change.Nonyl phenol is mainly derived from the biological degradation of nonionogenic tenside polyoxyethylene nonylphenol ether (NPEO), and polyoxyethylene nonylphenol ether is as home washings agent, industrial detergent, emulsifying agent etc., be widely used in weaving, leather, plastics, rubber and paper industry.Can say, this material has caused huge threat to multiplying and living of the mankind.Its content in water directly affects the security that water resources is utilized.In order to monitor accurately the content of nonyl phenol in water sample, need n nonylphenol to carry out effective pre-treatment.
At present, the beneficiation technologies for phenolic compound has: distillation method, microwave extraction method, liquid-liquid extraction method, liquid-phase micro-extraction method, solid phase extraction, Solid-phase Microextraction, supercritical extraction, liquid membrane separation method and molecularly imprinted polymer method etc.
Document 1 (Zhou Jianke, Peng Jing, dragon Kun. micro-extraction bottle enrichment-liquid chromatography for measuring underwater trace nonyl phenol [J]. Treatment of Industrial Water, 2011,30 (11): 77-79.) application self-control micro-extraction bottle, adopt octane-iso to make extraction agent, nonyl phenol in liquid-liquid micro-extracting method enrichment water, rp-hplc determination.Investigated different extraction agents, salting-out effect and the pH impact on effect of extracting.Selection octane-iso is extraction agent, NaCL concentration 30g/L, pH=4.5.The recovery of standard addition of nonyl phenol in water is 91.77%, and method detects and is limited to 0.525 μ g/L, and relative standard deviation is 1.82%.This extracting process is enrichment underwater trace nonyl phenol effectively.
Document 2 (Hongyi Zhang, Lihui Zhang, Shasha L.Subzero-Temperature Liquid-Liquid Extraction of Phenols for High-Performance Liquid Chromatography science research[J] .Conference on Environmental Pollution and Public Health, 2010,1007-1010.) use the aldehydes matter in the high-performance liquid chromatography method aqueous solution to comprise phenol, 4-nitrophenol, 2-nitrophenol, 2,4-chlorophenesic acid, dihydroxyphenyl propane.The water sample of 2ml acetonitrile (extraction agent) and 3.5ml is inserted in 10mL plastic centrifuge tube to whirlpool concussion 1min, freezing 30min at-30 ℃.Acetonitrile is through the organic worry membrane filtration of 0.45 μ m, sample introduction 5 μ L.Moving phase is the methanol aqueous solution of V (methyl alcohol): V (water)=55: 45; Sample size: 5 μ L; Flow velocity: 0.60mL/min: detect wavelength 285nm; C18 chromatographic column (250mm * 4.6mm, 5 μ m, Atlantis); Column temperature: 36 ℃.Record in Baoding tap water and Beijing tap water five kinds of phenolic compounds all lower than detection limit
(horse is strong for document 3, white birch, Wang Chao, Deng. high performance liquid chromatography, measure to the nonyl phenol in textiles and packaging material for food, octyl phenol and dihydroxyphenyl propane time [J]. analytical test journal, 2009,110 (128): 1160-1164.) set up the method that High Performance Liquid Chromatography/Photodiode Array Detection (DAD)/fluorimetric detector (FLD) serial connection technology is measured nonyl phenol, octyl phenol and dihydroxyphenyl propane in textiles and packaging material for food simultaneously.Employing accelerated solvent extraction is followed the example of, and take dehydrated alcohol as extracting solvent, and at 10.3Pa and 120 ℃, quiet cycle is extracted 2 times, and extracting solution is through Supelclean Envi-Carb graphitized carbon black Solid-Phase Extraction column purification, and LD series process detects.It is 225nm that the DAD of nonyl phenol, octyl phenol and dihydroxyphenyl propane detects wavelength, and fluorescence exciting wavelength is 227nm, and emission wavelength is 315nm.Under the interpolation level of 25,50,500 μ g/kg, the average recovery rate of textile samples and packaging material for food sample is 93%～98%, and relative standard deviation is respectively 218%～710% and 219%～619%.Method is accurate, easy, quick, can be used for the actual survey work of textiles and packaging material for food.
The problem that these methods exist has: the volatile and toxic property of the extraction liquid of liquid-liquid extraction method, liquid-phase micro-extraction method, and although solid phase extraction techniques and solid phase micro-extraction technique are most widely used, but there is poor repeatability, the not high and shortcoming of easily collecting not of selectivity.
Above-mentioned defect causes up to now, applies existing processing method and is difficult to obtain low price and reaction and requires that low, easy separation, reproducibility are good, the sorbent material of selective enrichment NP.
Summary of the invention
The invention provides a kind of magnetic molecularly imprinted polymer and preparation method, utilize magnetic molecularly imprinted material as sorbent material, the nonyl phenol in enrichment environmental water body simultaneously.
Technical solution of the present invention is:
A magnetic molecularly imprinted polymer, comprises magnetic substance Fe
3o
4with polybenzimidazole molecule, magnetic substance Fe wherein
3o
4be wrapped in polybenzimidazole molecule, be monocoque type, and/or be attached to polybenzimidazole molecular surface; Prepared by the concrete following steps that adopt:
(1) will under nonyl phenol and polybenzimidazole room temperature, be dissolved in N,N-dimethylacetamide;
(2) adopt molecular imprinting, take nonyl phenol as template molecule, take polybenzimidazole as function monomer, carry out trace, after trace finishes, add Fe
3o
4grind the dry magnetic molecule polymkeric substance that obtains;
(3) the magnetic molecule polymkeric substance obtaining in step (2) is used elutriant wash-out to remove template molecule, washing, makes magnetic molecularly imprinted polymer after being dried.
In step (1), the dosage of polybenzimidazole is 5～8.3g/L.
In step (1), the dosage of template molecule nonyl phenol is 0.017～0.05g/mL.
In step (3), elutriant is methyl alcohol: acetic acid (v/v)=99:1.
Magnetic Fe of the present invention
3o
4microballoon is to adopt a step thermal synthesis method to prepare.Embodiment is: by FeCl
3.6H
2o is dissolved in EG, forms clear liquid, after stirred for several hour, adds while stirring Co (NH)
2, glucose, mixed solution stirs for some time.Mixed solution is gone to autoclave stoichiometric number hour.Be cooled to repetitive scrubbing after room temperature, the magnetic microsphere of acquisition be placed in to baking oven dry.The magnetic Fe making
3o
4the particle diameter of microballoon is in 10-15 μ m left and right.
The present invention also provides the application of above-mentioned magnetic molecularly imprinted polymer, it is the Adsorption for water nonyl phenol by above-mentioned magnetic molecularly imprinted polymer, comprise the following steps: magnetic polybenzimidazole molecular imprinting adsorbing agent is added in the aqueous solution of nonyl phenol, pH is 2～10, temperature is controlled at 25～40 ℃, constant temperature oscillation adsorbs 5～1200min, measures the concentration of nonyl phenol in water after the separated removal of magnetic absorbent particles.
The features such as molecularly imprinted polymer of the present invention (MIPs) has strong interference immunity, selectivity is high, chemical stability good, long service life, cost are low, easy preparation, be a kind of polymer-function material target molecule to specific selectivity and recognition capability, in sample pre-treatments field, have a good application prospect.And make itself and Fe
3o
4magnetic nano-particle is in conjunction with generating after magnetic molecularly imprinted material, due to nanometer Fe
3o
4the characteristic such as special magnetic conductance tropism, superparamagnetism, just can make material both there is the feature of MIP " selectivity " absorption, there is again the separated feature of magneticsubstance " dynamically ", after completing the active absorption of template molecule and identification, can under additional the action of a magnetic field, from sample solution, separate at an easy rate.This makes the field of magnetic molecularly imprinted material nonyl phenol in enrichment processing environment water sample obtain development widely.
Soluble poly benzo imidazoles (PBI) in the present invention has suitable rigidity, certain flexibility and mechanical stability and thermostability, and few in the application in molecular imprinting field, therefore can deeply study.
Compared with prior art, its remarkable advantage is in the present invention:
(1) enrichment material has good chemical stability, does not have obvious desorption phenomenon.
(2) in Complex water body, interfering ion is a lot, adopts molecular imprinting, can make magnetic molecularly imprinted sorbent material have good selectivity to NP, and reach very soon adsorption equilibrium.Comparing aspect removal nonyl phenol, show significant superiority with non-molecular engram material (MNIP)
(3) magnetic molecularly imprinted sorbent material has magnetic, and after adsorption treatment, sorbent material can reclaim and recycling by foreign field;
(4) operating process of the present invention is simple, is easy to grasp.Therefore, the present invention has good economic benefit and application prospect for removing the nonyl phenol of environment water.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the adsorption effect contrast (pH is 6) of MMIP and MNIP n nonylphenol, and wherein transverse axis is the concentration of nonyl phenol in solution after adsorption equilibrium, the adsorptive capacity of MMIP and MNIP n nonylphenol.
Fig. 2 is the curve of adsorption kinetics of MMIP and MNIP n nonylphenol, and wherein transverse axis is adsorption time, the adsorptive capacity of MMIP and MNIP n nonylphenol.
Fig. 3 is MMIP and MNIP n nonylphenol, dihydroxyphenyl propane, tetrabromo-bisphenol, p-nitrophenol, phenol, the adsorption effect contrast of these five kinds of materials, and wherein the longitudinal axis is MMIP and the adsorptive capacity of MNIP to five kinds of materials.
Embodiment
A preparation method for magnetic polybenzimidazole molecular imprinting adsorbing agent, is characterized in that adopting following steps preparation:
(1) by 4.05g FeCl
3.6H
2o is dissolved in 160mlEG, forms clear liquid, stirs after 1 hour, adds while stirring 7g Co (NH)
2, 0.5g glucose, mixed solution stirs 30min.Mixed solution is gone to autoclave, at 200 ℃, react 10h.Be cooled to after room temperature, clarify, more thick solid is placed in to baking oven with straight alcohol and ultrapure water repetitive scrubbing to supernatant liquor, dry 6h, makes magnetic Fe at 55 ℃
3o
4microballoon.
(2) 0.2gNP is dissolved in and fills 6mLN, in the crucible of N-N,N-DIMETHYLACETAMIDE, after it all dissolves, add 0.035g soluble poly benzo imidazoles, continue to stir 6h, to clarified liq, become thickly, stop stirring.Inwardly add 0.30gFe
3o
4, with mortar alms bowl pestle, accelerate to be stirred to Fe
3o
4completely evenly be dissolved in viscous fluid, and viscous fluid can evenly spread upon crucible inside and not glide.Crucible is placed in to 55 ℃ of baking oven dried overnight.By the solid abrasive making to uniform microballoon powder.Powder is put into 100ml Erlenmeyer flask, add 60ml methyl alcohol: the mixing solutions of acetic acid (99:1), put into water bath with thermostatic control concussion case and carry out wash-out, 25 ℃ of eluting temperatures, rotating speed 155r/min, elution time 6h.The complete pressed powder of wash-out is put in dry 6h in the baking oven of 50 ℃, thereby makes MMIP.The preparation of MNIP, except not adding template molecule NP, all the other are identical with the preparation of MMIP.
The starting point concentration scope that the present invention is applicable to the nonyl phenol solution of processing is 0.01～2mg/L, and the consumption of sorbent material can be selected as the case may be.MMIP can be in acidity to the nonyl phenol in planar water under solutions of weak acidity.Adsorption time, pH and temperature have a certain impact to adsorption effect, can appropriately adjust according to actual conditions.
The preparation of magnetic molecularly imprinted sorbent material:
In the present embodiment, adsorptive capacity refers to the quality (mg/g) of the NP that every gram of sorbent material adsorbs.
Embodiment 1
0.2gNP is dissolved in the crucible that fills 6mL DMAc, after it all dissolves, adds 0.035g soluble poly benzo imidazoles, continue to stir 6h.Inwardly add 0.30gFe
3o
4, with mortar alms bowl pestle, accelerate to be stirred to Fe
3o
4completely evenly be dissolved in viscous fluid.Crucible is placed in to 55 ℃ of baking oven dried overnight.The powder obtaining is put into 100ml Erlenmeyer flask, adds 60ml methyl alcohol: the mixing solutions of acetic acid (99:1), and put into water bath with thermostatic control concussion case and carry out wash-out, 25 ℃ of eluting temperatures, rotating speed 155r/min, elution time 6h.The complete pressed powder of wash-out is put in dry 6h in the baking oven of 50 ℃, makes MMIP.
The preparation of MNIP, except not adding template molecule NP, all the other are identical with the preparation of MMIP.Take MMIP as enrichment material, the nonyl phenol in planar water.Be adsorbed on constant-temperature table and carry out.The starting point concentration of nonyl phenol is 100mg/L, and the pH value of solution is 6.2, and adsorption temp is 298K, and after absorption 6h, the adsorptive capacity of MMIP n nonylphenol is 70.9mg/g.
Comparative example 1
In embodiment 1, the non-molecular engram material of the magnetic of take (MNIP) is enrichment material, the nonyl phenol in planar water, and other adsorption conditions is constant, and the adsorptive capacity of MNIP n nonylphenol is 38.7mg/g.It the results are shown in Figure 1, Fig. 2.In figure, result shows, magnetic molecularly imprinted material is significantly increased than the adsorptive capacity of the non-molecular engram material n nonylphenol of magnetic.
Embodiment 2
In embodiment 1, the quality of polybenzimidazole is 5g/L, and other conditions are constant, and the adsorptive capacity that records MMIP n nonylphenol is 57.3mg/g.
Embodiment 3
In embodiment 1, the quality of polybenzimidazole is 8.3g/L, and other conditions are constant, and the adsorptive capacity that records MMIP n nonylphenol is 29.8mg/g.
Embodiment 4
In embodiment 1, the dosage 0.017g/mL of template molecule nonyl phenol wherein, other conditions are constant, and the adsorptive capacity that records MMIP n nonylphenol is 44.2mg/g.
Embodiment 5
In embodiment 1, the dosage 0.05g/mL of template molecule nonyl phenol wherein, other conditions are constant, and the adsorptive capacity that records MMIP n nonylphenol is 58.4mg/g.
Embodiment 6
In embodiment 1, when wherein the starting point concentration of nonyl phenol is 20mg/L, other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 23.1mg/g.
Embodiment 7
In embodiment 1, wherein the starting point concentration of nonyl phenol is 50mg/L, and other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 39.7mg/g.
Embodiment 8
In embodiment 1, wherein the pH value of nonyl phenol solution is 3.0 o'clock, and other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 58.1mg/g.
Embodiment 9
In embodiment 1, wherein the pH value of nonyl phenol solution is 6.0 o'clock, and other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 70.3mg/g.
Embodiment 10
In embodiment 1, when wherein adsorption time is 12h, other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 68.9mg/g.
Embodiment 11
In embodiment 1, when wherein adsorption time is 2h, other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 53.8mg/g.
Embodiment 12
In embodiment 1, when wherein adsorption temp is 313K, other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 54.3mg/g.
Embodiment 13
In embodiment 1, when wherein adsorption temp is 303K, other conditions are constant, and the adsorptive capacity of MMIP n nonylphenol is 65.3mg/g.
Embodiment 14
With MMIP and MNIP n nonylphenol, dihydroxyphenyl propane, tetrabromo-bisphenol, p-nitrophenol, phenol, these five kinds of materials adsorb, and adsorption conditions, with embodiment 1, records MMIP and the MNIP adsorptive capacity to five kinds of materials, and it the results are shown in Figure 3.In figure, result shows, MMIP will, apparently higher than other four kinds of structures, the similar material of character, illustrate that MMIP has good selectivity to the nonyl phenol in water to the adsorptive capacity of nonyl phenol in water.
Claims (9)
1. a magnetic molecularly imprinted polymer, is characterized in that, comprises magnetic substance Fe
3o
4with polybenzimidazole molecule, magnetic substance Fe wherein
3o
4be wrapped in polybenzimidazole molecule, be monocoque type, and/or be attached to polybenzimidazole molecular surface; Prepared by the concrete following steps that adopt:
(1) will under nonyl phenol and polybenzimidazole room temperature, be dissolved in N,N-dimethylacetamide;
(2) adopt molecular imprinting, take nonyl phenol as template molecule, take polybenzimidazole as function monomer, carry out trace, after trace finishes, add Fe
3o
4grind the dry magnetic molecule polymkeric substance that obtains;
(3) the magnetic molecule polymkeric substance obtaining in step (2) is used elutriant wash-out to remove template molecule, washing, makes magnetic molecularly imprinted polymer after being dried.
2. the method for synthesizing magnetic molecular engram material according to claim 1, is characterized in that: in step (1), the dosage of polybenzimidazole is 5～8.3g/L.
3. the method for synthesizing magnetic molecular engram material according to claim 1, is characterized in that: in step (1), the dosage of template molecule nonyl phenol is 0.017～0.05g/mL.
4. the method for synthesizing magnetic molecular engram material according to claim 1, is characterized in that: in step (3), elutriant is methyl alcohol: acetic acid (v/v)=99:1.
5. a preparation method for magnetic molecularly imprinted polymer, is characterized in that, said method comprising the steps of preparation:
(1) will under nonyl phenol and polybenzimidazole room temperature, be dissolved in N,N-dimethylacetamide;
(2) adopt molecular imprinting, take nonyl phenol as template molecule, the polybenzimidazole that the step (1) of take obtains is function monomer, carries out trace, after trace finishes, adds Fe
3o
4grind the dry magnetic molecule polymkeric substance that obtains;
(3) the magnetic molecule polymkeric substance obtaining in step (2) is used elutriant wash-out to remove template molecule, washing, makes magnetic molecularly imprinted polymer after being dried.
6. the method for synthesizing magnetic molecular engram material according to claim 5, is characterized in that: in step 1, the dosage of polybenzimidazole is 5～8.3g/L.
7. the method for synthesizing magnetic molecular engram material according to claim 5, is characterized in that: in step 1, the dosage of template molecule nonyl phenol is 0.017～0.05g/mL.
8. the method for synthesizing magnetic molecular engram material according to claim 5, is characterized in that: in step 3, elutriant is methyl alcohol: acetic acid (v/v)=99:1.
9. the application of a magnetic molecularly imprinted polymer, it is characterized in that, Adsorption by magnetic molecularly imprinted polymer claimed in claim 1 for water nonyl phenol, comprise the following steps: magnetic polybenzimidazole molecular imprinting adsorbing agent is added in the aqueous solution of nonyl phenol, pH is 2～10, temperature is controlled at 25～40 ℃, and constant temperature oscillation adsorbs 5～1200min, measures the concentration of nonyl phenol in water after the separated removal of magnetic absorbent particles.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911306A (en) * | 2012-10-10 | 2013-02-06 | 肇庆学院 | Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres |
| CN103558283A (en) * | 2013-11-18 | 2014-02-05 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of specific recognition nonylphenol sensor employing quaternary hybrid biomimetic composite material |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911306A (en) * | 2012-10-10 | 2013-02-06 | 肇庆学院 | Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres |
| CN103558283A (en) * | 2013-11-18 | 2014-02-05 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of specific recognition nonylphenol sensor employing quaternary hybrid biomimetic composite material |
Non-Patent Citations (1)
| Title |
|---|
| WEI MIN ZHONG ET AL.: "Study on the magnetic molecularly imprinted materials for removing the perfluorooctane sulfonate (PFOS) in water", 《ADVANCED MATERIALS RESEARCH》 * |
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Application publication date: 20141008 |