CN101613432A - A kind of molecular blotting polymer microsphere that is used for phenol and its production and application - Google Patents
A kind of molecular blotting polymer microsphere that is used for phenol and its production and application Download PDFInfo
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- CN101613432A CN101613432A CN200810115401A CN200810115401A CN101613432A CN 101613432 A CN101613432 A CN 101613432A CN 200810115401 A CN200810115401 A CN 200810115401A CN 200810115401 A CN200810115401 A CN 200810115401A CN 101613432 A CN101613432 A CN 101613432A
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Abstract
The invention provides a kind of molecular blotting polymer microsphere that is used for phenol, the polymer monomer of wherein said polymer microballoon is methacrylic acid or 4-vinylpridine, and the specific surface area of described polymer microballoon is 23.08-62.33m
2/ g.The present invention also provides a kind of method and the application of this polymer microballoon in enrichment or detection phenolic compound for preparing above-mentioned polymer microballoon.The present invention also provides chromatographic column and solid phase extraction column stuffing in addition, and this filler is described molecular blotting polymer microsphere.Molecular blotting polymer microsphere preparation of the present invention is simple, convenient, the adsorption selectivity of the polymer microballoon of molecular imprinting of the present invention is at 8.25-44.55mg/g simultaneously, and reached balance in 6 hours, this polymer microballoon has the adsorption selectivity height, the advantage that rate of adsorption is fast.
Description
Technical field
The present invention relates to a kind of molecular blotting polymer microsphere that is used for phenol and its production and application.Belong to environmental monitoring and processing technology field.
Background technology
(molecularly imprinted polymer is under the linking agent effect MIP) to molecularly imprinted polymer, and the effect of template molecule and function monomer produces a kind of technology that the chemo-selective binding site is arranged.Substrate to be measured is by be identified coincideing aspect the location of shape, size and functional group with the template molecule polymkeric substance.MIP can analyze the technology coupling with liquid chromatography, capillary electrophoresis, capillary electrochromatography, Solid-Phase Extraction etc.In recent years, the MIP with high selectivity becomes a flourish new problem in the applied research aspect the sample analysis such as medicine, biochemistry and environment.
Molecularly imprinted polymer is a kind of novel high polymer biomimetic material with strong molecule distinguishability.The preparation of molecularly imprinted polymer generally will be passed through following three steps: (1) makes between template molecule and monomer molecule to be measured with the covalently or non-covalently form generation complementary interaction of key, formation mixture; (2) add linking agent, around template-monomer complex, carry out polyreaction; (3) template molecule in the polymkeric substance of removal polyreaction formation.Because the adding of template molecule in polymerization process, behind the template molecule in the flush away polymkeric substance, will stay some holes in template polymer, the distribution of its size, shape and functional group and monomer to be measured have complementarity, thereby monomer to be measured is had selectivity.Its process stays the trace of template molecule as branding on polymkeric substance.
Because the method for molecular imprinting is simple, easy handling, adsorption selectivity are strong, therefore, has represented good prospects for application in fields such as environment measuring, clinical medicine analysis, bionical sensings rapidly.According to the character of the adducts that forms between function monomer and template, exist the molecular imprinting method of two kinds of forms, i.e. covalency blotting and non-covalent blotting.The formed title complex of covalency blotting is very stable, and exists equivalent relation each other, but the synthetic comparatively difficulty of title complex is simultaneously also uneconomical, and is therefore successful like that not as the latter in actual applications.Non-covalent blotting needn't synthon-template title complex, can under the condition of gentleness template molecule be removed from polymkeric substance, and the bonding of object all has very fast speed with disengaging.Noncovalent interaction commonly used has: hydrogen bond, electrostatic attraction, metal-chelating effect, charge transfer, hydrophobic interaction and Van der Waals force etc., use at most with hydrogen bond.Non-covalent blotting has become the main direction of molecular imprinting research in recent years, and its polymerization methods has mass polymerization, in-situ polymerization, suspension polymerization, precipitation polymerization etc. several.
Wherein, suspension polymerization normally adds initiator in the mixing solutions that monomer, pore-creating agent and dispersion agent are formed, and under agitation the polyreaction that causes between monomer to be measured and the template molecule through free radical produces spherical insoluble polymer.Advantage is by adjusting polymerizing condition, size and size distribution that can controlling polymers microballoon micropore, and the molecular weight of product and distribute narrowly, the regularity and the monodispersity of product are also fine simultaneously.Since be solid particulate, therefore separation, dry convenient, and granular resin can directly use.
Have characteristics such as affinity and selectivity height, anti-adverse environment ability are strong, good stability, long service life, applied range based on molecularly imprinted polymer, therefore, it in a lot of fields, represented good prospects for application as fields such as chromatographic separation, Solid-Phase Extraction, bionical sensing, mimetic enzyme catalysis, clinical medicine analysis, absorption, membrane sepn, and become polymer chemistry thus, one of the emerging field of cross discipline research such as biological chemistry and Materials science.
Phenolic compound can be by skin and gastrointestinal absorption, and the phenolic compound after the absorption mainly is distributed in liver, blood, kidney and lung.Phenolic compound is a prototype matter poisonous substance, to all toxic effect of all bionts.Phenolic compound can be invaded inside of human body by contact, suction and the oral administration of skin, mucous membrane.When it contacts with protein in the cell magma, chemical reaction can take place, form insoluble protein, and cell is lost vigor.Phenol can also continue to internal penetration, causes deep tissues damage, necrosis, poisons until whole body.In the ocean, phenol can produce various toxic effects to waterplant, suppresses algae grows, and simultaneously, the substituting group of phenol is many more, and is big more to the toxicity of fish.The chlorophenol material is that purposes is the widest in the phenolic compound, toxicity is big, pollutes a more serious compounds.It is mainly derived from the pollution in the use, as the discharging as sterilant, wood preservative and trade effluent, for example pulp bleaching effluent.Because chlorophenol has certain dissolubility in water, and because its octanol water partition coefficient is bigger, it is significantly fat-soluble that 1gKow is that 2.17-5.01 has, and can accumulate in biosphere by food chain, thereby aggravate their contaminative greatly.For these reasons, a lot of in the world countries such as the U.S., European Union, Japan and China all classify chlorophenol as priority pollutant.Because phenol is to the hazardness of environment, China is with the 2,4 dichloro phenol in the chlorophenol compound, 2,4, and 6-Trichlorophenol and pentachlorophenol are classified priority pollutants in the water body as.
2,4, the 6-trichlorophenol, molecular formula is C
6H
3Cl
3O, its molecular weight is 197.44, belongs to dangerous substances, sucking, take in or after skin absorption, health being harmful to, eyes, skin, mucous membrane and the upper respiratory tract there are hormesis, its powder and air can form explosive mixture, when reaching finite concentration, meet Mars and can blast.Be subjected to the pyrolytic decomposition poisonous gas of emitting.Has corrodibility.Can produce following harmful products of combustion: carbon monoxide, carbonic acid gas, hydrogenchloride.Its acute toxicity data is as follows: LD
50: 820mg/kg, rat is oral.Also with 2,4, the 6-trichlorophenol divides the 6.1st class poisonous substances in the classification of using hazardous chemical always and standard GB13690-92.
2,4-two chlorophenols, molecular formula is C
6H
4Cl
2O, its molecular weight is 163.00, belongs to dangerous substances, sucking, take in or after skin absorption health being harmful to, eyes, skin, mucous membrane and the upper respiratory tract is had hormesis.Environment there is harm, flammable, in flame, discharge pungency or toxic smog or gas; Decomposite during burning and contain chloride of acid and acid anhydrides is poisonous and irritant gas.Its acute toxicity data is as follows: LD
50: 580 mg/kg rats are oral.Animal poisons to test the performance of tic.
The 4-chlorophenol, white, needle-shaped crystals has the smell of phenol, is soluble in alcohol, ether, glycerine and chloroform, is slightly soluble in water and whiteruss, and molecular formula is C
6H
5ClO, its molecular weight is 28.56, belongs to dangerous substances, sucking, take in or after skin absorption health being harmful to, eyes, skin, mucous membrane and the upper respiratory tract is had hormesis.Environment there is harm, flammable, in flame, discharge pungency or toxic smog or gas; Decomposite during burning and contain chloride of acid and acid anhydrides is poisonous and irritant gas.Its acute toxicity data, LD
50: the 670mg/kg rat is oral.
The ordinary method of handling chlorophenol pollutants has light-intensity method, paper chromatography, thin plate chromatography, vapor-phase chromatography, liquid chromatography and GC-MS(gas chromatography-mass spectrography) etc., and is the most common with high performance liquid chromatography.But because chlorophenol is difficult adsorbed by conventional C-18 sorbent material, use efficient liquid phase chromatographic analysis, be difficult to the concentration effect that reaches satisfied.Therefore, developing a kind of P-Chlorophenol compound has the sorbing material of unique absorption property to become the focus of everybody concern at present.
Although the molecular imprinting speed of development is than very fast at present, and has obtained using more widely, when using, reality still has many problems.At first, the form of the mechanism of action of the mechanism of molecular imprinting process and molecular recognition process and sign problem, binding site, polymkeric substance and mass transport mechanism remain the problem that investigators pay close attention to.Secondly, using and selecting of function monomer, linking agent and polymerization process commonly used at present all has bigger limitation, therefore at specific template molecule, for example 2 among the present invention, 4,6-trichlorophenol, 2, the imprinted polymer microballoon of 4-two chlorophenols or 4-chlorophenol molecule, yet there are no report in the prior art, this just makes molecular imprinting can not satisfy the needs of practical application far away.
Simultaneously, the polymerization precursor can not evenly spread in the dispersion agent during existing preparation molecular blotting polymer microsphere, so it is also inhomogeneous to obtain the grain diameter of polymer microballoon, therefore as high performance liquid chromatography (HPLC) situation that chromatographic peak is wide and trail usually appears when stationary phase detects monomer to be measured as MIP, reduce thereby post is imitated, influenced separating effect.Therefore, need preparation to have the molecular blotting polymer microsphere of uniform grading.
Summary of the invention
A purpose of the present invention provides a kind of molecular blotting polymer microsphere that is used for phenol.
Another object of the present invention provides the method for the described molecular blotting polymer microsphere of preparation.
Still a further object of the present invention provides the application of described polymer microballoon in enrichment or detection phenolic compound.
A further object of the present invention provides a kind of chromatographic column filler, and this chromatographic column filler adopts molecular blotting polymer microsphere of the present invention.
A further object of the present invention provides a kind of solid phase extraction column stuffing, and this solid phase extraction column stuffing adopts molecular blotting polymer microsphere of the present invention.
The invention provides a kind of molecular blotting polymer microsphere that is used for phenol, the polymer monomer of described polymer microballoon is methacrylic acid or 4-vinylpridine, and the specific surface area of described polymer microballoon is 23.08-62.33m
2/ g.
Preferably, the pore volume of described polymer microballoon is 0.08-0.14cm
3/ g.
Preferably, the aperture of described polymer microballoon is 70-104
Preferably, the particle diameter of described polymer microballoon is 2-3.2 μ m.
Preferably, described phenol is the chlorophenol compound.
Preferably, described chlorophenol compound is selected from 2,4,6-trichlorophenol, 2, a kind of in 4-two chlorophenols and the 4-chlorophenol.Molecular formula is as follows:
2,4,6-trichlorophenol 2,4-two chlorophenol 4-chlorophenols.
The present invention also provides a kind of method for preparing described polymer microballoon, and this method may further comprise the steps:
A. function monomer and template molecule are dissolved in the solvent, obtain mixing solutions, described function monomer is selected from a kind of in methacrylic acid and the 4-vinylpridine, and described template molecule is a phenolic compound, and described solvent is acetonitrile or propionitrile;
B. in described mixing solutions, add linking agent and initiator, mix;
C. remove the oxygen in the mixing solutions that contains linking agent and initiator, add dispersion agent in the mixing solutions of removing oxygen, carry out polyreaction, described dispersion agent is a paraffin;
D. remove the template molecule in the polymeric reaction product that step c obtains, obtain described polymer microballoon.
Preferably, described solvent is an acetonitrile.
In preparation molecularly imprinted polymer of the present invention, be that dispersion medium is not suitable for synthetic with the non-covalent imprinted polymer of hydrogen bonded with water, because water can disturb the generation of hydrogen bond between template molecule and the function monomer, whiteruss is that dispersion medium can solve this difficult problem.But for needing the preceding mixing solutions of polymerization, the dispersion medium Synthesis of Molecular Imprinting Polymers in whiteruss, do not dissolve with whiteruss.Find that in experiment chloroform, methylene dichloride and toluene can both be dissolved in the whiteruss, have only the acetonitrile or third solvent to be not dissolved in whiteruss simultaneously again as solvent preferably.Therefore, all adopting whiteruss in experiment is dispersion medium, and acetonitrile or propionitrile are solvent, are preferably acetonitrile.
Preferably, the volume ratio of the mixing solutions of described removal oxygen and described paraffin is 1: 4-1: 15.
Preferably, wherein the linking agent described in the step b is selected from Vinylstyrene, Ethylene glycol dimethacrylate, N, N '-methylene radical diacrylate amine, N, N '-1,4-phenylene diacrylamine, 3, a kind of in 5-diacrylamine yl benzoic acid, L-2-diacrylamine base phenylpropyl alcohol acrylate, pentaerythritol triacrylate and the trimethylolpropane trimethacrylate.
Preferably, the polymeric reaction product that in described steps d step c is obtained is centrifugal, removes supernatant liquor, obtains solids, extracts to remove the phenolic compound in this solids with acetonitrile-acetic acid mixed solution Soxhlet, and drying obtains described polymer microballoon.
Preferably, the volume ratio of acetonitrile-acetate is 90: 10 in described acetonitrile-acetic acid mixed solution.
Preferably, in described step a, a kind of and phenolic compound in methacrylic acid and the 4-vinylpridine is with 4-8: 1 molar ratio is dissolved in the organic nitrile solvent.
Preferably, in described step b, in described mixing solutions, add the linking agent of 20-40 times of molar weight of phenolic compound and the initiator of 0.5-1 times of molar weight.
Preferably, described initiator is selected from a kind of in Diisopropyl azodicarboxylate, azo two isonitrile and the 2,2'-Azobis(2,4-dimethylvaleronitrile).
The present invention provides the application of a kind of described molecular blotting polymer microsphere in enrichment or detection phenolic compound again.
The present invention provides a kind of chromatographic column filler again, and described chromatographic column filler is formed by described polymer microballoon.
The present invention provides a kind of solid phase extraction column stuffing again, and described solid phase extraction column stuffing is formed by described polymer microballoon.
Principles of Polymerization among the present invention are as follows:
The technique effect that the present invention produced is:
Molecular blotting polymer microsphere preparation of the present invention is simple, convenient; This polymer microballoon that is used for the phenol molecular imprinting is even, and specific surface area reaches 23.08-62.33m
2/ g, pore volume reaches 0.08-0.14cm
3/ g, with respect to the existing polymer microballoon that is used for the phenol molecular imprinting, the adsorption selectivity of the polymer microballoon of molecular imprinting of the present invention is at 8.25-44.55mg/g, and has and select rate of adsorption faster, reaches balance in 6 hours.With of the present invention a kind of preferred embodiment be example, in this embodiment, use 2,4,6-trichlorophenol, 2,4-two chlorophenols or 4-chlorophenol are as template molecule, methacrylic acid is a function monomer, Vinylstyrene is a linking agent, uv-light polymerization under the effect of Diisopropyl azodicarboxylate initiator, and obtaining particle diameter is the molecular imprinting microsphere polymer microballoon with higher selective adsorption performance of 2-3 μ m.This polymer microballoon has 62.33m
2The specific surface area of/g, 0.14cm
3The pore volume of/g and suitable with molecular size 70.02
The aperture, to 2,4,6-trichlorophenol, 2, phenolic compound molecules such as 4-two chlorophenols and 4-chlorophenol have extremely strong selective adsorption performance, the maximum selectivity adsorptive capacity is 44.55mg/g, and rate of adsorption faster reached the Static Adsorption balance in 6 hours substantially, can be used in the environmental sample 2,4,6-trichlorophenol, 2, the enrichment and the detection of phenolic compound molecules such as 4-two chlorophenols and 4-chlorophenol.And this polymer microballoon can directly experimentize in water surrounding, need not too much other organic reagent, environmental friendliness; In addition, molecular blotting polymer microsphere rate of adsorption of the present invention is fast.Molecularly imprinted polymer of the present invention is as the chromatographic stationary phase, promptly during chromatograph packing material, can reduce post and press, and improves post and imitates, and enlarged the Application Areas of molecular imprinting.
The present invention prepares the suspension polymerization that molecular blotting polymer microsphere adopts, can obtain particle diameter evenly, big, the specific selectivity of specific surface area adsorbs tangible molecular engram microsphere.Compare with the dispersion polymerization processes in the suspension polymerization, the common suspension polymerization that adopts among the present invention need not add stablizer, the therefore polymer microballoon surface cleaning that obtains, and can avoid by the non-selective absorption to template molecule of stablizer or tensio-active agent.Compare with bulk polymerization, it is easy, convenient that the suspension polymerization that adopts among the present invention prepares, and do not need processes such as loaded down with trivial details polymkeric substance grinds, sieves, and cost is low, and the trace effect might as well.Therefore, as novel molecular imprinting polymerization technique, suspension polymerization will have broad application prospects.Polymer microballoon of the present invention generally is applied to the processing and the monitoring of environmental water sample, particularly described molecular blotting polymer microsphere with selective adsorption performance and off-line or online mode and ultraviolet-visible spectrophotometry, liquid chromatography, liquid chromatography-mass spectrography etc. are analyzed Instrument crosslinking, environmental water sample is handled and monitored.This polymkeric substance can off-line or is analyzed Instrument crosslinkings with ultraviolet-visible spectrophotometry, liquid chromatography, liquid chromatography-mass spectrography etc. online, will have broad application prospects in the context of detection of environmental pollution, analytical chemistry etc.
Particularly, because molecular blotting polymer microsphere particle diameter of the present invention is even, from the scanning electron microscope of Fig. 2 as can be seen molecular blotting polymer microsphere of the present invention particle diameter, simultaneously can observe its degree of scatter, micro polymer spherical diameter of the present invention is 2-3 μ m, specific surface area is big, has very strong selective adsorption performance.Can be used as solid phase extraction column stuffing and be used for 2,4 of off-line enrichment environment sample, 6-trichlorophenol, 2, phenolic compound such as 4-two chlorophenols and 4-chlorophenol detect in conjunction with ultraviolet-visible spectrophotometry, liquid chromatography, liquid chromatography-mass spectrography; Can be used as chromatographic column filler 2,4 in the chromatographic column on-line preconcentration environmental sample of packing into, 6-trichlorophenol, 2, phenolic compound such as 4-two chlorophenols and 4-chlorophenol detect in conjunction with liquid chromatography, liquid chromatography-mass spectrography.The preparation of this polymkeric substance and use all very simply, convenient, enrichment in application, to separate phenolic compound speed fast, and selectivity is good, and the efficient height will have broad application prospects in the context of detection of environmental pollution, analytical chemistry etc.
Description of drawings
Fig. 1 is the schema of the method for preparation molecular blotting polymer microsphere of the present invention.
Fig. 2 is the stereoscan photograph of molecular blotting polymer microsphere of the present invention.
Fig. 3 is the isothermal adsorption dynamic experiment result of molecularly imprinted polymer of the present invention, and curve from top to bottom was followed successively by 0 minute, 10 minutes, and 30 minutes, 2.0 hours, 6.0 hours, the sorption isotherm of 16.0 hours molecularly imprinted polymer.
Embodiment
Embodiment 1
With 1 mole 2,4, the 6-trichlorophenol is a template molecule, and 4 moles of methacrylic acids are function monomer, are dissolved in the 4ml acetonitrile solvent, obtain mixing solutions; In described mixing solutions, add 2,4, the Vinylstyrene of 20 times of molar weights of 6-trichlorophenol is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.66 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 12mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the molecular imprinting microsphere polymer of white.Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2,4, and the 6-trichlorophenol is that the maximum selectivity adsorptive capacity of template molecule is 44.55mg/g.The specific surface area of the polymer microballoon that obtains is 62.33m
2/ g, particle diameter are 2.8 μ m, and pore volume is 0.14cm
3/ g, the aperture is 73.02
Molecular blotting polymer microsphere by present embodiment makes is used as chromatographic column and solid phase extraction column stuffing, can enrichment and detection 2,4,6-trichlorophenol.
Accurately take by weighing the 5.0g molecularly imprinted polymer, add 2,4 of 20mL200mg/L, room temperature vibration in the 6-trichlorophenol aqueous solution, respectively at 10 minutes, 30 minutes, 2 hours, 6 hours, 16 hours solution centrifugals, get supernatant liquor and detect, obtain the isothermal adsorption dynamic experiment result of polymkeric substance, see Fig. 3 by ultraviolet-visible spectrophotometer.By experimental result as can be known, can reach adsorption equilibrium at 6 hours.
The molecular formula of methacrylic acid, Vinylstyrene and Diisopropyl azodicarboxylate is as follows in the present embodiment
Methacrylic acid Vinylstyrene Diisopropyl azodicarboxylate
Embodiment 2
With 1 mole 2,4, the 6-trichlorophenol is a template molecule, and 4 moles of 4-vinylpridines are function monomer, are dissolved in the 4ml acetonitrile solvent, obtain mixing solutions; In described mixing solutions, add 2,4, the L-2-diacrylamine base phenylpropyl alcohol acrylate of 20 times of molar weights of 6-trichlorophenol is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.8 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 27mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the molecular imprinting sub-micro ball polymkeric substance 2.5 μ m of white.The specific surface area of the polymer microballoon that obtains is 26.97m
2/ g, pore volume are 0.082cm
3/ g, the aperture is 90.34
Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2,4, and the 6-trichlorophenol is that the maximum selectivity adsorptive capacity of template molecule is 9.67mg/g.
Embodiment 3
With 1 mole 2,4, the 6-trichlorophenol is a template molecule, and 6 moles of methacrylic acids are function monomer, is dissolved in the 4ml propionitrile solvent, obtains mixing solutions; In described mixing solutions, add 2,4, the Ethylene glycol dimethacrylate of 30 times of molar weights of 6-trichlorophenol is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.5 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 18mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the molecular imprinting sub-micro ball polymkeric substance 2.8 μ m of white.The specific surface area of the polymer microballoon that obtains is 23.08m
2/ g, pore volume are 0.089cm
3/ g, the aperture is 104.82
Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2,4, and the 6-trichlorophenol is that the maximum selectivity adsorptive capacity of template molecule is 6.56mg/g.
Embodiment 4
With 1 mole 2,4, the 6-trichlorophenol is a template molecule, and 8 moles of methacrylic acids are function monomer, are dissolved in the 4ml acetonitrile solvent, obtain mixing solutions; In described mixing solutions, add 2,4, the trimethylolpropane trimethacrylate (TRIM) of 40 times of molar weights of 6-trichlorophenol is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 1 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 21mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the particle diameter 3.2 μ m of the molecular blotting polymer microsphere of white.The specific surface area of the polymer microballoon that obtains is 30.65m
2/ g, pore volume are 0.094cm
3/ g, the aperture is 96.53
Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2,4, and the 6-trichlorophenol is that the maximum selectivity adsorptive capacity of template molecule is 33.40mg/g.
Embodiment 5
With 1 mole 2,4, the 6-trichlorophenol is a template molecule, and 4 moles-vinyl pyridine is a function monomer, is dissolved in the 4ml acetonitrile solvent, obtains mixing solutions; In described mixing solutions, add 2,4, the pentaerythritol triacrylate of 20 times of molar weights of 6-trichlorophenol is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.66 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 27mL whiteruss, mix and be placed on 60 ℃ of thermal-initiated polymerizations 24 hours, obtain molecular imprinting microsphere polymer.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens.The specific surface area of the polymer microballoon that obtains is 43.27m
2/ g, particle diameter are 2.0 μ m, and pore volume is 0.11cm
3/ g, the aperture is 80.24
Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2,4, and the 6-trichlorophenol is that the maximum selectivity adsorptive capacity of template molecule is 12.79mg/g.
Embodiment 6
With 1 mole 2,4-two chlorophenols are template molecule, and 4 moles of methacrylic acids are function monomer, are dissolved in the 4ml acetonitrile solvent, obtain mixing solutions; In described mixing solutions, add 2,4,3 of 20 times of molar weights of 6-trichlorophenol, 5-diacrylamine yl benzoic acid is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.66 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 30mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the molecular imprinting microsphere polymer of white.The specific surface area of the polymer microballoon that obtains is 57.48m
2/ g, particle diameter are 3.2 μ m, and pore volume is 0.12cm
3/ g, the aperture is 78.54
Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2, and 4-two chlorophenols are that the maximum selectivity adsorptive capacity of template molecule is 32.76mg/g.
Embodiment 7
With 1 mole of 4-chlorophenol is template molecule, and 4 moles of methacrylic acids are function monomer, are dissolved in the 4ml acetonitrile solvent, obtain mixing solutions; In described mixing solutions, add 2,4, the Vinylstyrene of 20 times of molar weights of 6-trichlorophenol is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.66 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 33mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the molecular imprinting microsphere polymer of white.The specific surface area of the polymer microballoon that obtains is 53.89m
2/ g, particle diameter are 2.7 μ m, and pore volume is 0.11cm
3/ g, the aperture is 72.66
Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is that the maximum selectivity adsorptive capacity of template molecule is 8.25mg/g to the 4-chlorophenol.
Embodiment 8
With 1 mole 2,4, the 6-trichlorophenol is a template molecule, and 4 moles of methacrylic acids are function monomer, are dissolved in the 4ml acetonitrile solvent, obtain mixing solutions; In described mixing solutions, add 2,4,20 times of molar weights of 6-trichlorophenol, N, N '-methylene radical diacrylate amine is as linking agent and 2,4, the Diisopropyl azodicarboxylate that 6-trichlorophenol molar weight is 0.8 times mixes as initiator, and logical nitrogen deoxidation 10min is to remove dissolved oxygen in the mixing solutions.Get above-mentioned solution 3mL and add in the 39mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.To react the centrifugal 3500rpm of resulting mixture, 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain the molecular imprinting microsphere polymer of white.Above-mentioned molecular imprinting microsphere polymer has tangible specific adsorption, and it is to 2,4, and the 6-trichlorophenol is that the maximum selectivity adsorptive capacity of template molecule is 44.55mg/g.
Embodiment 9
Following experiment flow is used for preparing embodiment of the present invention to 2,4, and the 6-trichlorophenol has selective adsorption performance molecular imprinting microsphere polymer.
(1) suspension polymerization process: with 1mmol 2,4, the 6-trichlorophenol is dissolved in the acetonitrile of 4ml, adds the N of 4mmol, N '-1, and 4-phenylene diacrylamine, ultrasonic 30min mixes it fully, and forms non-covalent monomer-template title complex.In above mixing solutions, add the 20mmol Vinylstyrene, the 0.66mmol Diisopropyl azodicarboxylate, ultrasonic 30min mixes it fully.Logical nitrogen deoxidation 10min is to remove dissolved oxygen.Get above-mentioned solution 3mL and add in the 45mL whiteruss, mix and be placed under the UV-irradiation polyreaction 24 hours.
(2) wash-out of template molecule: will react resulting mixture at 3500rpm, centrifugal 20min, abandoning supernatant, solids acetonitrile-acetic acid mixed solution (90: 10, v/v) Soxhlet is extracted, and does not have 2,4 in extracting solution, and the 6-trichlorophenol detects.Resulting solids is dried in 40 ℃ of vacuum drying ovens, promptly obtain 2,4 of white, 6-6-trichlorophenol molecular imprinting polymkeric substance.
Following flow process is used for the evaluation and the sign of polymkeric substance of the present invention: utilize scanning electron microscope to record its particle diameter, can observe its degree of scatter simultaneously; Utilize the specific surface area analysis instrument can record its specific surface area, pore volume and aperture, adsorption experiment can record the microspheroidal polymkeric substance to 2,4, the selective adsorption capacity of 6-trichlorophenol.Adsorption experiment carries out at aqueous phase, and purpose is in order to be used for water body 2,4 later on, the processing of 6-trichlorophenol and monitoring.The evaluation of polymkeric substance more of the present invention and characterization result data summary of the invention have in front partly carried out associated description.Here only exemplarily provide the evaluation and the characterization result data of wherein a kind of preferred polymkeric substance (being aforesaid typical polymers):
The performance measurement result of table 1, preferred molecularly imprinted polymer of the present invention
Claims (13)
1. molecular blotting polymer microsphere that is used for phenol, the polymers function monomer of described polymer microballoon is methacrylic acid or 4-vinylpridine, and the specific surface area of described polymer microballoon is 23.08-62.33m
2/ g.
2. polymer microballoon according to claim 1, the pore volume of wherein said polymer microballoon are 0.08-0.14cm
3/ g.
3. polymer microballoon according to claim 1 and 2, the aperture of wherein said polymer microballoon are 70-
4. according to each described polymer microballoon among the claim 1-3, the particle diameter of wherein said polymer microballoon is 2-3.2 μ m.
5. according to each described method among the claim 1-4, wherein said phenol is the chlorophenol compound, and this chlorophenol compound is preferably selected from 2,4,6-trichlorophenol, 2, a kind of in 4-two chlorophenols and the 4-chlorophenol.
6. method for preparing each described polymer microballoon among the claim 1-5, this method may further comprise the steps:
A. function monomer and template molecule are dissolved in the solvent, obtain mixing solutions, described function monomer is selected from a kind of in methacrylic acid and the 4-vinylpridine, and described template molecule is a phenolic compound, and described solvent is acetonitrile or propionitrile, preferred acetonitrile;
B. in described mixing solutions, add linking agent and initiator, mix;
C. remove the oxygen in the mixing solutions that contains linking agent and initiator, add dispersion agent in the mixing solutions of removing oxygen, carry out polyreaction, described dispersion agent is a paraffin, preferably, the volume ratio of the mixing solutions of described removal oxygen and described paraffin is 1: 4-1: 15;
D. remove the template molecule in the polymeric reaction product that step c obtains, obtain described polymer microballoon.
7. method according to claim 6, wherein the linking agent described in the step b is selected from Vinylstyrene, Ethylene glycol dimethacrylate, N, N '-methylene radical diacrylate amine, N, N '-1,4-phenylene diacrylamine, 3, a kind of in 5-diacrylamine yl benzoic acid, L-2-diacrylamine base phenylpropyl alcohol acrylate, pentaerythritol triacrylate and the trimethylolpropane trimethacrylate.
8. according to claim 6 or 7 described methods, wherein the polymeric reaction product that in described steps d step c is obtained is centrifugal, remove supernatant liquor, obtain solids, extract to remove the phenolic compound in this solids with acetonitrile-acetic acid mixed solution Soxhlet, drying obtains described polymer microballoon, and preferably, the volume ratio of acetonitrile-acetate is 90: 10 in described acetonitrile-acetic acid mixed solution.
9. according to each described method among the claim 6-8, wherein in described step a, a kind of and phenolic compound in methacrylic acid and the 4-vinylpridine is with 4-8: 1 molar ratio is dissolved in the organic nitrile solvent.
10. according to each described method among the claim 6-9, wherein in described step b, in described mixing solutions, add the linking agent of 20-40 times of molar weight of phenolic compound and the initiator of 0.5-1 times of molar weight, preferably, described initiator is selected from a kind of in Diisopropyl azodicarboxylate, azo two isonitrile and the 2,2'-Azobis(2,4-dimethylvaleronitrile).
11. the application of each described molecular blotting polymer microsphere in enrichment or detection phenolic compound among the claim 1-5.
12. a chromatographic column filler, it is formed by each described polymer microballoon among the claim 1-5.
13. a solid phase extraction column stuffing, it is formed by each described polymer microballoon among the claim 1-5.
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