CN101234329A - SiO2 granule surface molecule print adsorption agent and preparation thereof - Google Patents
SiO2 granule surface molecule print adsorption agent and preparation thereof Download PDFInfo
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- CN101234329A CN101234329A CNA2008100466612A CN200810046661A CN101234329A CN 101234329 A CN101234329 A CN 101234329A CN A2008100466612 A CNA2008100466612 A CN A2008100466612A CN 200810046661 A CN200810046661 A CN 200810046661A CN 101234329 A CN101234329 A CN 101234329A
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Abstract
The invention provides a molecular blot absorbent of a SiO2 particle surface in a water phase system and a preparation method thereof, which overcomes the defects of low identification ability and low service life caused by mismatched solvent polarity or by using toxic organic solvent in synthesis in the prior art. The preparation method is provided with the following steps: firstly, activating treatment is adopted to SiO2 particles, and the particles react with a functional monomer and target phenolic pollutants such as one of chlorophenols or nitrophenol to form a complex type precursor body; the molecular blot absorbent of the SiO2 particle surface is obtained through polymerization and post treatment after the re-oxidation. The molecular blot absorbent of the invention is simple in preparation technique and low in cost; the absorbent has high selectivity in target molecules, a fast balancing speed in absorption and de-sorption and can be repeatedly used.
Description
Technical field
The present invention relates to a kind of SiO
2Granule surface molecule print adsorption agent and preparation method thereof, particularly SiO in the whole water phase system
2Granule surface molecule print adsorption agent and preparation method thereof.
Technical background
Phenolic compound is a class important chemical material, is widely used as bactericide, herbicide, pesticide and timber preservative.Phenolic compound is easy to enrichment in animal body, causes animal's liver, kidney and neurotrosis.Being extensive use of of phenolic compound caused soil and underground water pollution in the world wide.Therefore, phenolic compound has great importance in enrichment detection and the removal environment.
The mensuration of trace phenolic compound needs enrichment usually in the environmental sample.Enrichment method commonly used at present has liquid-liquid extraction and SPE.Comparatively speaking, the more traditional liquid-liquid extraction of SPE has more advantage: enrichment speed is very fast, organic solvent consumption is few, little to the pollution of environment, simple to operate, is easy to automation etc.But traditional solid phase extraction column all is to adopt nonpolar C
18The SiO of modification
2Particle is as filler, and is all poor for the concentration effect and the selectivity of the phenolic compound of middle polarity.Therefore, design and the synthetic sorbing material that phenolic compound is had high selectivity and a high enrichment multiple have crucial meaning.
(Molecular Imprinting Technique MIT) is one of the main method of current development high selectivity material to molecular imprinting.MIT is meant the character of the shape of specific molecular and the electric charge, hydrophobicity, hydrogen bond receptor and the donor that distribute on the molecular surface process of trace in the polymer complementally, (Molecular Imprinted polymer MIP) can keep by the shape of microsphere and molecular surface character the molecularly imprinted polymer that obtains.Trace in the polymer with had special corresponding relation by the molecule of trace, have the effect of memory template molecular shape, thus make the imprinted polymer material have identification specific molecular performance.
Up to now, document and patent are more about the report of molecular engram.But the work of the molecular engram aspect of relevant phenolic compound is less, particularly at pure aqueous phase in SiO
2The work of the molecular engram aspect of the phenolic compound of particle surface does not appear in the newspapers as yet.Yan Xiuping, Korea Spro must completely wait (number of patent application 200510013736.3) adsorbing material of pentachlorophenol with stamp amino functionality on surface of silicon boll that adopted molecular engram and sol-gel technology preparing, through hcl as extraction agent the masterplate molecule is removed, on modification silicon ball, stayed special hole, the material that is synthesized has higher selectivity to pentachlorophenol, but they are silicon ball sorbing materials synthetic in organic solvent ethanol.Cheng Guoxiang, Zhang Lishui (number of patent application 02121484.0) discloses and has a kind ofly utilized emulsion polymerization technology to prepare the method for molecular engram microsphere in water and toluene blending agent, utilize the synthetic MIP microspherulite diameter of this method to adjust as required, good molecular recognition performance is arranged.In general, all adopting methacrylic acid in the tradition synthetic molecules trace adsorbent method is function monomer, ethylene glycol dimethacrylate is a crosslinking agent, azodiisobutyronitrile is an initator, thereby generally need be at the organic system of low pole or middle polarity (as toluene, chloroform, acetone, ethanol etc.) or in the oil hydrosol system carry out, when practical application molecular imprinting adsorbing agent separation and concentration or detection target organic pollution generally then is in the aqueous environment of strong polarity, like this because not the matching of solvent polarity in building-up process and the use, to cause molecular imprinting adsorbing agent in use its volume swelling or blockage effect may take place, thereby greatly influence its recognition capability and service life to target molecule.In addition, in synthetic MIP process, need to use in a large number poisonous and hazardous organic solvent, not only contaminated environment, and increase manufacturing cost.Therefore, press for the synthetic technology of research molecular engram in the whole water phase system.
The inventor had once applied for patent of invention: " artificial anitibody type composite photocatalyst and preparation method thereof " (application number: be with titanium dioxide (TiO 200610019453.4)
2) as matrix, o-phenylenediamine is function monomer and crosslinking agent, organic pollutant molecule is a template molecule, under uv-light polymerization, successfully prepared artificial anitibody type composite photocatalyst, this invention is specially at the high selectivity degraded of the organic pollution of high toxicity low concentration, the selectivity degradation effect is very good, but this composite catalyst is not a sorbing material.The present invention is the synthetic SiO that the phenols target contaminant is had special adsorptive selectivity in the pure water phase system
2Granule surface molecule print adsorption agent specifically is with SiO
2Particle is as matrix, and o-phenylenediamine is function monomer and crosslinking agent, and organic phenolic comp ' ds pollution molecule is a template molecule, and initiated polymerization under the effect of initator persulfate makes SiO
2Granule surface molecule print type adsorbent.Synthetic good SiO
2Granule surface molecule print adsorption agent can fill in solid phase extraction column, specially at the high selectivity preferential adsorption enrichment and the analysis of organic phenolic comp ' ds pollution of high toxicity low concentration, this invention has solved this technical barrier of synthetic molecules trace type adsorbent under the water condition.
Summary of the invention
The objective of the invention is to use in a large amount of poisonous organic solvents and the use because solvent polarity does not match the recognition capability that causes when the synthetic molecules trace type adsorbent and degradation shortcoming under service life, thereby SiO in a kind of whole water phase system is provided at prior art
2Granule surface molecule print adsorption agent and preparation method thereof.
SiO of the present invention
2Granule surface molecule print adsorption agent, its kernel is SiO
2Matrix, outer core are to be skeleton, to be the compound adsorbent of microsphere with target phenolic comp ' ds pollution to be adsorbed that with the conducting polymer composite that the function monomer polymerization obtains particle diameter is 10～20 microns a particle.
SiO of the present invention
2Granule surface molecule print type preparation of adsorbent method is as follows:
(1) to SiO
2Particle carries out priming reaction: in function monomer and silicon atom mol ratio is that 0.01%～250% ratio is with SiO
2It is 0.01～2mol L that particle joins concentration
-1NaOH solution in, be 25 ℃～60 ℃ stirring reaction 10～100min in temperature, wash to eluent for neutral, suction filtration; SiO with gained
2It is 0.01～6mol L that particle joins concentration
-1HCl solution in, be 25 ℃～40 ℃ stirring reaction 10～200min in temperature, wash to eluent for neutral, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) with the SiO of step (1) gained
2Particle is 0.5%～25% to join the ethanolic solution that volume ratio is 2%～15% 3-aminopropyl triethoxysilane with silicon atom and ethanol mol ratio, in temperature is 25 ℃～60 ℃ stirring reaction 6～15h, remove unreacted 3-aminopropyl triethyl silicane with the ethanol washing, suction filtration, vacuum drying obtains amidized SiO
2Particle;
(3) in reactor, add function monomer and target phenolic comp ' ds pollution, the mol ratio of target contaminant and function monomer is 0.02%～200%, in reactor, add distilled water again, in temperature is 25 ℃～60 ℃ stirring reaction 10～60min, makes target contaminant and function monomer form compound type presoma with chemical bond;
(4) be 0.075%～100% ratio adds step (2) gained in reactor SiO in function monomer and silicon atom mol ratio
2Particle, ultrasonic dispersion 5～15min makes suspension;
(5) regulate above-mentioned pH of suspension value to 2～6 with hydrochloric acid, the temperature of control solution is that 10%～200% ratio is with 0.2～1mol L in function monomer and initator mol ratio in 25 ℃～60 ℃ scopes
-1Initator in 20～60min, be added drop-wise in this suspension stirring reaction 5～24h;
(6) by particle after the suction filtration collection modification, be 0.001～0.5mol L with concentration
-1Na
2CO
3Solution washing 5～6 times with distilled water washing 8～10 times, with the oven dry of gained particle, promptly gets SiO again
2Granule surface molecule print adsorption agent.
Above-mentioned said function monomer is selected from following a kind of or both mixture: thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and derivative class thereof.
Thiophene and derivative class thereof specifically are meant: thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-(2-methyl butyl) thiophene, 3,4-dibromo thiophene;
Pyrroles and derivative class thereof specifically are meant: pyrroles, N-methylpyrrole, pyrrolidones, N-vinyl pyrrolidone;
Aniline and derivative class thereof specifically are meant: aniline, o-toluidine, 3,3 '-dimethoxy benzidine, 3,3 '-dimethylbenzidine, o-phenylenediamine, 2-chloroaniline, p-phenylenediamine (PPD).
Above-mentioned said target phenolic comp ' ds pollution is selected from: one of chlorophenols, nitropheneol;
Chlorophenols specifically is meant: 2-chlorophenol, 4-chlorophenol, 2,4-two chlorophenols, 2,6-two chlorophenols, pentachlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol;
Nitropheneol specifically is meant: 2-nitrophenols, 4-nitrophenols and 2,4-dinitrophenol dinitrophenolate.
The function monomer that step (3) adds in reactor: be arbitrarily one or two kind in thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and the derivative class thereof; General function monomer and silicon atom mol ratio are 0.075%～100%, and the ratio between one or the two kind of function monomer of adding is arbitrarily.
The initator of step (5) indication is meant: Ammonium Persulfate 98.5, potassium peroxydisulfate, sodium peroxydisulfate.
Confirmed SiO by infrared, uv drs, thermogravimetric etc.
2There is the molecularly imprinted polymer thin layer really in particle surface, and its outer nuclear mass accounts for total mass ratio and is approximately 1%～20%;
The SiO that the present invention obtains
2Granule surface molecule print adsorption agent can be made into SiO
2-MIP solid phase extraction column is set up the MIP-SPE-HPLC analytical method with the HPLC coupling, is used for the mensuration of actual water sample phenolic compound.Can be used as SiO
2The substitute of particle also can adopt fine particles such as hollow glass.Because various function monomer structure differences, the structure of the polymer that forms is also inequality with relevant physicochemical properties, and multiple monomer carries out copolymerization, can be in structure and play the effect of complementation in nature, help to improve the adsorption capacity of MIP to target molecule.
The SiO that the present invention makes
2Surface molecule print type adsorbent can directly be used commercially available SiO
2Particle is a base material, and preparation technology is simple, does not have harsh synthesis condition requirement, and is with low cost.Its scope of using pH of synthetic sorbing material is wide, and target molecule is had high selectivity, and the adsorption/desorption balancing speed is fast, and is reusable.These advantages have guaranteed that this adsorbent can highly selective enrichment and identification phenolic comp ' ds pollution, thus the environmental pollution of administering these pollutants effectively and being caused.
This method specifically is earlier function monomer to be mixed in the aqueous solution of certain pH value with target contaminant, and the generation presoma that makes it to react, and adds amidized micron SiO in the presoma of gained
2Particle, polymerization reaction take place and be coated on SiO under the effect of initator persulfate
2Particle surface.Embodiment is prepared to 2, and the 4-dinitrophenol dinitrophenolate has the poly-o-phenylenediamine/SiO of specific selectivity
2Graininess surface molecule print type adsorbent is made the MIP-SPE pillar as SPE (SPE) filler, with high performance liquid chromatography (HPLC) coupling, sets up the MIP-SPE-HPLC analytical method, is used for the enrichment and the analysis of actual water sample phenolic comp ' ds pollution.Its rate of recovery is more than 92%, RSD＜2.8%; And adopt traditional C
18The rate of recovery of-SPE is less than 30%, and RSD is 3.0%, and the result shows: the molecular imprinting adsorbing agent that the present invention makes has high selectivity to target molecule, and the rate of recovery and RSD result obviously are better than traditional C
18-SPE analysis result.
Description of drawings
Fig. 1 SiO
2Particle, amination SiO
2The infared spectrum of particle and MIP.
Ordinate is a transmitance, and abscissa is wavelength (nm).
Fig. 2 SiO
2Particle, amination SiO
2The uv drs collection of illustrative plates of particle and MIP.
Outer diffuse reflection collection of illustrative plates; Curve 3 is represented the uv drs collection of illustrative plates of MIP.
Ordinate is a reflectivity, and abscissa is wavelength (nm).
Fig. 3 SiO
2Particle, amination SiO
2The thermogravimetric collection of illustrative plates of particle, MIP and NIP.Curve 1 is represented SiO
2The thermogravimetric collection of illustrative plates of particle; Curve 2 is represented amination SiO
2The thermogravimetric collection of illustrative plates of particle; Curve 3 is represented the thermogravimetric collection of illustrative plates of MIP; Curve 4 is represented the thermogravimetric collection of illustrative plates of NIP.Ordinate is that quality varies with temperature rate (dm/dT), abscissa be temperature (℃).
Fig. 4 target molecule 2,4-dinitrophenol dinitrophenolate on MIP and NIP adsorption capacity with change in concentration figure.Adopt 20 mg SiO respectively
2-MIP and SiO
2-NIP adsorbent, absorption original concentration scope is 50～350mg L
-12,4-dinitrophenol dinitrophenolate solution;
Fig. 5 selective absorption 2, the chromatogram of 4-dinitrophenol dinitrophenolate.
Adopt SiO respectively
2-MIP and C
18Be solid phase extraction filler, make MIP-SPE and C
18-SPE pillar, original concentration are 1.0mg L
-12,4-dinitrophenol dinitrophenolate and 10.0mg L
-1The phenol mixed liquor.
Curve a represents mixed liquor direct injected chromatogram, and curve b represents mixed liquor through C
18Chromatogram after the 5 times of-SPE enrichments, curve c represent mixed liquor through the chromatogram after 5 times of the MIP-SPE enrichments, and retention time 2.2min and 2.8min are corresponding respectively 2,4-dinitrophenol dinitrophenolate and phenol.
Ordinate is voltage (mV), and abscissa is time (min).
The specific embodiment
Example 1:(1) in beaker, adds 3g SiO
2And 50mL 0.25mol L
-1NaOH solution is 25 ℃ of stirring reaction 60min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 2.0mol L
-1In the HCl solution, be 25 ℃ of stirring reaction 60min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 1g is activated
2Particle joins the ethanolic solution that volume ratio is 5% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 12h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) add 2 of the o-phenylenediamine of 0.01mol and 0.001mol in another beaker, the 4-dinitrophenol dinitrophenolate adds 100mL distilled water again, is 45 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 1g
2Particle, ultrasonic dispersion 10min makes suspension;
(5) the pH value of regulator solution is 2.5, and the temperature of control solution is 45 ℃, drips 25mL 0.2mol L in 30min
-1Ammonium Persulfate 98.5 solution, stirring reaction 12h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.025mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtains a kind ofly to 2 at last, and the 4-dinitrophenol dinitrophenolate has the SiO of specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 2:(1) in beaker, adds 12g SiO
2And 50mL 0.5mol L
-1NaOH solution is 45 ℃ of stirring reaction 10min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 1.0mol L
-1In the HCl solution, be 40 ℃ of stirring reaction 60min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 10g is activated
2Particle joins the ethanolic solution that volume ratio is 2% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 15h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) add 2 of the aniline of 0.1mol and 0.001mol in another beaker, 6-two chlorophenols add 50mL distilled water again, are 50 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 6g
2Particle, ultrasonic dispersion 5min makes suspension;
(5) the pH value of regulator solution is 3.0, and the temperature of control solution is 50 ℃, drips 25mL 0.5mol L in 40min
-1Ammonium Persulfate 98.5 solution, stirring reaction 12h;
(6) with the particle particle suction filtration after the modification, use 0.05mol L
-1Na
2CO
3Solution washing particle particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtain at last a kind of to 2, the SiO that 6-two chlorophenols have the specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 3:(1) in beaker, adds 6g SiO
2And 50mL 1.0mol L
-1NaOH solution is 25 ℃ of stirring reaction 30min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 2.0mol L
-1In the HCl solution, be 35 ℃ of stirring reaction 200min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 2g is activated
2Particle joins the ethanolic solution that volume ratio is 6% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 6h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) adding the o-phenylenediamine of 0.1mol and the 4-nitrophenols of 0.05mol in another beaker, add 75mL distilled water again, is 45 ℃ of stirring reaction 60min in temperature;
(4) in beaker, add the amidized SiO of 1.5g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 3.8, and the temperature of control solution is 45 ℃, drips 25mL 0.4mol L in 60min
-1Sodium peroxydisulfate solution, stirring reaction 10h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.1mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle obtains a kind of SiO that the 4-nitrophenols is had the specific selectivity adsorption capacity at last at 80 ℃ of dry 2h
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 4:(1) in beaker, adds 6g SiO
2And 50mL 2.0mol L
-1NaOH solution is 35 ℃ of stirring reaction 30min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 0.01mol L
-1In the HCl solution, be 30 ℃ of stirring reaction 180min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 5g is activated
2Particle joins the ethanolic solution that volume ratio is 10% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 10h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) add 2 of the monomer pyrroles of the o-phenylenediamine of 0.005mol and 0.005mol and 0.02mol in another beaker, the 4-dinitrophenol dinitrophenolate adds 150mL distilled water again, is 60 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 5g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 3.5, and the temperature of control solution is 25 ℃, Dropwise 35 mL 0.4mol L in 60min
-1Ammonium Persulfate 98.5 solution, stirring reaction 15h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.001mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtains a kind ofly to 2 at last, and the 4-dinitrophenol dinitrophenolate has the SiO of specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 5:(1) in beaker, adds 6g SiO
2And 50mL 1.0mol L
-1NaOH solution is 35 ℃ of stirring reaction 30min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 0.5mol L
-1In the HCl solution, be 25 ℃ of stirring reaction 50min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 1.5g is activated
2Particle joins the ethanolic solution that volume ratio is 3% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 12h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) adding the o-phenylenediamine of 0.005mol and the pentachlorophenol of 0.000001mol in another beaker, add 100mL distilled water again, is 55 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 0.8g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 4.0, and the temperature of control solution is 55 ℃, drips 25mL 0.2mol L in 20min
-1Potassium persulfate solution, stirring reaction 15h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.5mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtains a kind ofly to 2 at last, and the 4-dinitrophenol dinitrophenolate has the SiO of specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 6:(1) in beaker, adds 6g SiO
2And 50mL 1.0mol L
-1NaOH solution is 28 ℃ of stirring reaction 100min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 1.5mol L
-1In the HCl solution, be 30 ℃ of stirring reaction 60min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 1g is activated
2Particle joins the ethanolic solution that volume ratio is 7% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 12h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) add 2,4 of 3,3 of 0.00001mol '-dimethoxy benzidine and 0.00002mol in another beaker, the 6-trichlorophenol adds 50mL distilled water again, is 35 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 0.8g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 3.6, and the temperature of control solution is 35 ℃, drips 25mL 0.3mol L in 45min
-1Potassium persulfate solution, stirring reaction 24h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.025mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtains a kind ofly to 2,4 at last, and the 6-trichlorophenol has the SiO of specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 7:(1) in beaker, adds 1g SiO
2And 50mL 1.0mol L
-1NaOH solution is 25 ℃ of stirring reaction 80min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 2.0mol L
-1In the HCl solution, be 25 ℃ of stirring reaction 150min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 1g is activated
2Particle joins the ethanolic solution that volume ratio is 12% 3-aminopropyl triethoxysilane, is 50 ℃ of following stirring reaction 12h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) adding the N-vinyl pyrrolidone of 0.01mol and the 2-nitrophenols of 0.002mol in another beaker, add 100mL distilled water again, is 35 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 0.8g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 5.3, and the temperature of control solution is 35 ℃, drips 25mL 0.2mol L in 30min
-1Ammonium Persulfate 98.5 solution, stirring reaction 24h;
(6) with the SiO after the modification
2The particle suction filtration is with 0.025 mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle obtains a kind of SiO that the 2-nitrophenols is had the specific selectivity adsorption capacity at last at 80 ℃ of dry 2h
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 8:(1) in beaker, adds 12g SiO
2And 50mL 1.5mol L
-1NaOH solution is 25 ℃ of stirring reaction 60min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 3.0mol L
-1In the HCl solution, be 25 ℃ of stirring reaction 100min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 1g is activated
2Particle joins the ethanolic solution that volume ratio is 8% 3-aminopropyl triethoxysilane, is 60 ℃ of following stirring reaction 10h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) monomer 3 of adding 0.5mol in another beaker, 2,4 of 4-dibromo thiophene and 0.0005mol, the 5-trichlorophenol adds 100mL distilled water again, is 65 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 0.8g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 3.2, and the temperature of control solution is 65 ℃, drips 25mL 0.35mol L in 45min
-1Sodium peroxydisulfate solution, stirring reaction 18h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.04mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtains a kind ofly to 2,4 at last, and the 5-trichlorophenol has the SiO of specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 9:(1) in beaker, adds 6g SiO
2And 50mL 1.0mol L
-1NaOH solution is 45 ℃ of stirring reaction 75min in temperature, and it is neutral washing to eluent, suction filtration.SiO with gained
2Particle joins 50mL 4.0mol L
-1In the HCl solution, be 25 ℃ of stirring reaction 30min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 3g is activated
2Particle joins the ethanolic solution that volume ratio is 13% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 12h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) adding the aniline of 0.025mol and the 2-chlorophenol of 0.05mol o-toluidine and 0.0005mol in another beaker, add 100mL distilled water again, is 55 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 2.5g
2Particle, ultrasonic dispersion 15min makes suspension;
(5) the pH value of regulator solution is 6.0, and the temperature of control solution is 60 ℃, drips 10mL 1mol L in 50min
-1Ammonium Persulfate 98.5 solution, stirring reaction 24h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.025mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle obtains a kind of SiO that the 2-chlorophenol is had the specific selectivity adsorption capacity at last at 80 ℃ of dry 2h
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Example 10:(1) in beaker, adds 4g SiO
2And 50mL 0.8mol L
-1NaOH solution is 60 ℃ of stirring reaction 45min in temperature, and it is neutral washing to eluent, suction filtration.With the SiO after the washes clean
2Particle joins 50mL 6.0mol L
-1In the HCl solution, be 40 ℃ of stirring reaction 10min in temperature, it is neutral washing to eluent, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) SiO that 2g is activated
2Particle joins the ethanolic solution that volume ratio is 15% 3-aminopropyl triethoxysilane, is 40 ℃ of following stirring reaction 9h in temperature, removes unreacted 3-aminopropyl triethoxysilane with the ethanol washing, suction filtration, and vacuum drying obtains amidized SiO
2Particle;
(3) add 2 of the N-methylpyrrole of 0.5mol and 0.02mol N-vinyl pyrrolidone and 0.0005mol in another beaker, the 4-dinitrophenol dinitrophenolate adds 100mL distilled water again, is 25 ℃ of stirring reaction 30min in temperature;
(4) in beaker, add the amidized SiO of 1.8g
2Particle, ultrasonic dispersion 10min makes suspension;
(5) the pH value of regulator solution is 2.0, and the temperature of control solution is 25 ℃, Dropwise 5 0mL 0.2mol L in 40min
-1Potassium persulfate solution, stirring reaction 28h;
(6) with the SiO after the modification
2The particle suction filtration is used 0.025mol L
-1Na
2CO
3Solution washing SiO
2Particle 5 times is again with distilled water washing 8 times.With SiO
2Particle is at 80 ℃ of dry 2h, obtains a kind ofly to 2 at last, and the 4-dinitrophenol dinitrophenolate has the SiO of specific selectivity adsorption capacity
2Base molecular engram type adsorbent.Synthetic imprinted polymer is inserted solid phase extraction column, be used for the enrichment and the analysis of actual water sample phenolic compound.
Claims (4)
1. SiO
2Granule surface molecule print adsorption agent, its kernel is SiO
2Matrix, outer core are to be skeleton, to be the compound adsorbent of microsphere with target phenolic comp ' ds pollution to be adsorbed with the conducting polymer composite that the function monomer polymerization obtains.
2. the preparation method of the molecular imprinting adsorbing agent of claim 1, concrete synthesis step is:
(1) to SiO
2Particle carries out priming reaction: in function monomer and silicon atom mol ratio is that 0.01%～250% ratio is with SiO
2It is 0.01～2mol L that particle joins concentration
-1NaOH solution in, be 25 ℃～60 ℃ stirring reaction 10～100min in temperature, wash to eluent for neutral, suction filtration; SiO with gained
2It is 0.01～6mol L that particle joins concentration
-1HCl solution in, be 25 ℃～40 ℃ stirring reaction 10～200min in temperature, wash to eluent for neutral, suction filtration, oven dry, the SiO that obtains activating
2Particle;
(2) with the SiO of step (1) gained
2Particle is 0.5%～25% to join the ethanolic solution that volume ratio is 2%～15% 3-aminopropyl triethoxysilane with silicon atom and ethanol mol ratio, in temperature is 25 ℃～60 ℃ stirring reaction 6～15h, remove unreacted 3-aminopropyl triethyl silicane with the ethanol washing, suction filtration, vacuum drying obtains amidized SiO
2Particle;
(3) in reactor, add function monomer and target phenolic comp ' ds pollution, the mol ratio of target contaminant and function monomer is 0.02%～200%, in reactor, add distilled water again, in temperature is 25 ℃～60 ℃ stirring reaction 10～60min, makes target contaminant and function monomer form compound type presoma with chemical bond;
(4) be 0.075%～100% ratio adds step (2) gained in reactor SiO in function monomer and silicon atom mol ratio
2Particle, ultrasonic dispersion 5～15min makes suspension;
(5) regulate above-mentioned pH of suspension value to 2～6 with hydrochloric acid, the temperature of control solution is that 10%～200% ratio is with 0.2～1mol L in function monomer and initator mol ratio in 25 ℃～60 ℃ scopes
-1Initator in 20～60min, be added drop-wise in this suspension stirring reaction 5～24h;
(6) by particle after the suction filtration collection modification, be 0.001～0.5mol L with concentration
-1Na
2CO
3Solution washing 5～6 times with distilled water washing 8～10 times, with the oven dry of gained particle, promptly gets SiO again
2Granule surface molecule print adsorption agent.
3. according to the molecular imprinting adsorbing agent of claim 1 or the preparation method of claim 2, the function monomer of indication is selected from following a kind of or both mixture: thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and derivative class thereof;
Thiophene and derivative class thereof specifically are meant: thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-(2-methyl butyl) thiophene, 3,4-dibromo thiophene;
Pyrroles and derivative class thereof specifically are meant: pyrroles, N-methylpyrrole, pyrrolidones, N-vinyl pyrrolidone;
Aniline and derivative class thereof specifically are meant: aniline, o-toluidine, 3,3 '-dimethoxy benzidine, 3,3 '-dimethylbenzidine, o-phenylenediamine, 2-chloroaniline, p-phenylenediamine (PPD).
Said target phenolic comp ' ds pollution is selected from: one of chlorophenols, nitropheneol;
Chlorophenols specifically is meant: 2-chlorophenol, 4-chlorophenol, 2,4-two chlorophenols, 2,6-two chlorophenols, pentachlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol;
Nitropheneol specifically is meant: 2-nitrophenols, 4-nitrophenols and 2,4-dinitrophenol dinitrophenolate.
4. according to the preparation method of claim 2, the function monomer that above-mentioned steps (3) adds in reactor: be arbitrarily one or two kind in thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and the derivative class thereof; General function monomer and silicon atom mol ratio are 0.075%～100%, and the ratio between one or the two kind of function monomer of adding is arbitrarily;
The initator of step (5) indication specifically is meant: Ammonium Persulfate 98.5, potassium peroxydisulfate, sodium peroxydisulfate.
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