CN103626906B - A kind of alternative identifies the synthetic method of the hydrophilic polymer microballoon of tsiklomitsin - Google Patents
A kind of alternative identifies the synthetic method of the hydrophilic polymer microballoon of tsiklomitsin Download PDFInfo
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- CN103626906B CN103626906B CN201310511087.4A CN201310511087A CN103626906B CN 103626906 B CN103626906 B CN 103626906B CN 201310511087 A CN201310511087 A CN 201310511087A CN 103626906 B CN103626906 B CN 103626906B
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Abstract
The present invention relates to the synthetic method that a kind of alternative identifies the hydrophilic polymer microballoon of tsiklomitsin, belong to environment functional material technical field.The present invention with nontoxic, free of contamination ethanol for green solvent, tsiklomitsin is template molecule, methacrylic acid is function monomer, vinylbenzene and trimethylolpropene acid esters are cross-linked polymeric monomer, Diisopropyl azodicarboxylate is for causing precipitation polymerization, postpone to add hydrophilic polymeric monomers hydroxyethyl methylacrylate, one kettle way prepares hydrophilic molecular engram polymer microballoon.The invention provides simple one kettle way, the hydrophilic molecular engram polymer microballoon of synthesis performance excellence, in water surrounding, the selective removal of tetracycline residue provides a kind of novel material and environment-friendly preparation method thereof thereof.
Description
Technical field
The present invention relates to the synthetic method that a kind of alternative identifies the hydrophilic polymer microballoon of tsiklomitsin, belong to technical field of environmental material preparation.
Background technology
Tetracycline antibiotics is the disease prevention and the treatment that are widely used in human and animal, digest and assimilate difference in vivo, major part does not participate in metabolism and gets rid of external, it is caused to accumulate in the environment and enrichment, after people take in the water and food that tetracycline residue exceeds standard for a long time, tsiklomitsin slowly can be accumulated in human body, produces toxic side effect, cause the pathology of the multiple organ of human body to human body.In ecotope, tetracycline residue is confirmed by Chinese scholars research.Dimension, the efficient means that tetracycline residue in environment is removed in development and application just becomes particularly important.Adsorption method of separation is the most frequently used method, and adsorptive capacity is large, rate of adsorption is fast, adsorption selectivity is high, equipment is simple, easy to operate etc.
Molecular imprinting is preparation has single-minded recognition capability polymkeric substance method to a certain specific molecular, and the polymkeric substance of preparation is called molecularly imprinted polymer.The preparation process of polymkeric substance is generally: template molecule and function monomer form the mixture with certain space structure by covalently or non-covalently key, trace polymerization is there is subsequently under the effect of initiator and linking agent, finally by template molecule wash-out from highly cross-linked converging network, leave binding site template molecule to single-minded recognition reaction in imprinted polymer, this site has special affinity and selectivity to template molecule.Molecularly imprinted polymer has been widely used in the selective removal of pollutent in water surrounding.
Conventional molecular imprinted polymer is obtained by mass polymerization mostly, have to pass through pulverizing, grinding and screening and obtain the particle wanted, the loaded down with trivial details and particle that obtains of this method process usually pattern and size is irregular, loading capacity is low and template molecule is difficult to close.Adopt suspension polymerization, Two-step seed swelling method and precipitation polymerization method can obtain the molecular imprinting polymerization ball of relative particle size uniform.Wherein precipitation polymerization method because not adding any stablizer in reaction system, avoids stablizer or tensio-active agent to the impact of trace; Component is simple, processing ease; Not only can avoid numerous and diverse aftertreatment, size distribution is comparatively even, good dispersity, and adhesion phenomenon is less, and trace hole is exposed to the advantages such as the probability of microsphere surface is large.Therefore, precipitation polymerization method has been applied to the preparation of molecular blotting polymer microsphere.But current precipitation polymerization is mainly polymerized in the toxic solvent such as acetonitrile, toluene, and studies less in innoxious solvent second alcohol and water.Therefore, develop the green solvent system being applicable to prepare molecularly imprinted polymer and have great Research Significance.Most of pollutent is extensively present in water surrounding, in water surrounding, how effectively to identify that with being separated be problem urgently to be resolved hurrily.Hydrophilic molecular engram polymer can address this problem preferably.
Summary of the invention
The object of this invention is to provide the synthetic method of hydrophilic polymer microballoon that a kind of alternative identifies tsiklomitsin, the hydrophilic molecular engram polymer microballoon prepared by the method to the Selective recognition of tsiklomitsin in water surrounding be separated.
The present invention relates to the synthetic method that a kind of alternative identifies the hydrophilic polymer microballoon of tsiklomitsin, belong to environment functional material technical field.The present invention with nontoxic, free of contamination ethanol for green solvent, tsiklomitsin is template molecule, methacrylic acid is function monomer, vinylbenzene and trimethylolpropene acid esters are cross-linked polymeric monomer, Diisopropyl azodicarboxylate is for causing precipitation polymerization, postpone to add hydrophilic polymeric monomers hydroxyethyl methylacrylate, one kettle way prepares hydrophilic molecular engram polymer microballoon.By the physicochemical property of the instrumental characterizing hydrophilic molecular engram polymer microballoons such as infrared spectrometer, field emission scanning electron microscope, size distribution instrument and contact angle measurement.Adsorption experiment is utilized to carry out institute system for hydrophilic molecular engram polymer microballoon to the adsorption equilibrium of tsiklomitsin, kinetics and adsorption selectivity performance.
the technical solution used in the present invention is:
The alternative synthetic method identifying the hydrophilic polymer microballoon of tsiklomitsin, carry out according to following step:
According to tsiklomitsin (TC): methacrylic acid (MAA): trimethylolpropane trimethacrylate (TMPTMA): the mol ratio of vinylbenzene (St) is 1:(3-6): (24-48): the ratio of (40-50) (mmol/mmol/mmol/mmol), adds tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate successively in round-bottomed flask.According to vinylbenzene: the mass ratio of ethanol is 1:(50-100) ratio of (g/g), in flask, add ethanol, ultrasonic disperse, form homogeneous phase solution.Under room temperature, the pre-assembled 12-24 hour of lucifuge; Ultrasonic degas, logical nitrogen 20-30min, according to Diisopropyl azodicarboxylate (AIBN): the mass ratio of ethanol is (0.02-0.04): the ratio of 100 (g/g), Diisopropyl azodicarboxylate is added as initiator in solution, flask is placed in water bath with thermostatic control vibrator, rotating speed is from 25 in 100-200r/min, 1.0h
oc is warming up to 60
oc, precipitation polymerization reaction 12h; According to hydroxyethyl methylacrylate (HEMA): the mass ratio of ethanol is (0.01-0.03): the ratio of 100 (g/g), adds hydroxyethyl methylacrylate, 60 in system
oc continues oscillatory reaction 12h.After reaction terminates, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; Be the methyl alcohol of 9:1 by volume ratio: acetic acid mixture surname extraction 6h, repeatedly, eluted template molecule, to elutriant ultraviolet-visible pectrophotometer can't detect tsiklomitsin, with ethanol and distilled water by product washing to neutral, 60
ounder C, vacuum-drying is to constant weight, obtains hydrophilic molecular engram polymer microballoon (HMIMs).Take same preparation method, but do not add tsiklomitsin in process as template molecule, obtain the non-imprinted polymer microballoon (HNIMs) of wetting ability.If in polymerization process, do not add hydroxyethyl methylacrylate and participate in polymerization, obtain molecular blotting polymer microsphere (MIMs); If not methylate Hydroxyethyl acrylate and tsiklomitsin, obtain non-imprinted polymer microballoon (NIMs).
Technological merit of the present invention: ethanol is as polymer solvent, nontoxic, pollution-free is green polymerization system; Polymer microballoon prepared by precipitation polymerization does not need loaded down with trivial details last handling process, can directly use; By postponing the method adding hydroxyethyl methylacrylate, realize the wetting ability of imprinted polymer microballoon, and imprinted sites is not destroyed; Hydrophilic molecular engram polymer microballoon has good selectivity to tsiklomitsin in water surrounding, can be applied to the selective removal of tetracycline residue in actual water sample.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of Fig. 1 MIMs (a), HMIMs (b), NIMs (c) and HNIMs (d).As can be known from Fig. 1: NIMs particle is the spherical of monodispersity, and size is relatively homogeneous, is about 2.1um, and HNIMs size slightly increases, and keeps spherical; MIMs and HMIMs particle presents irregular form, and agglomeration is serious, and infer thus, in polymerization process, adding of template molecule creates larger impact to the pattern of polymer particle.
The infrared spectrogram of Fig. 2 HMIMs and HNIMs.As can be known from Fig. 2: 1730cm
-1the stretching vibration peak of C=O, 2940cm
-1and 2981cm
-1for-CH
2with-CH
3stretching vibration peak, 3544cm
-1the broad peak at place and 1223cm
-1the weak peak at place, illustrates that HEMA is successfully introduced the extexine of polymkeric substance.
The grain size distribution of Fig. 3 HMIMs and HNIMs.As can be known from Fig. 3: HMIMs size distribution is wider, HNIMs narrow diameter distribution, major part concentrates on about 2.1um, and this result is with to obtain conclusion in Fig. 1 consistent.
The water contact angle figure (A) of Fig. 4 MIMs (a) and HMIMs (b); Scatter diagram (B) in the water of MIMs (a), HMIMs (b), NIMs (c) and HNIMs (d).Known from Fig. 4 A: the water contact angle of MIMs and HMIMs is respectively 149.92 ± 0.1 ° and 59.58 ± 0.2 °, illustrate that delay adds hydroxyethyl methylacrylate and participates in polymerization, the HMIMs prepared has good wetting ability; In Fig. 4 B, HMIMs and HNIMs has good dispersiveness in water proves that HEMA is successfully introduced polymeric outer surface again.
Fig. 5 solution ph is on the impact of HMIMs and HNIMs tetracycline adsorption.As can be seen from Figure 5: when pH value is 5.0, adsorptive capacity reaches maximum value, therefore, the optimal ph of solution is 5.0.
Fig. 6 HMIMs and HNIMs is to the adsorption isothermal line matched curve figure of tsiklomitsin.As can be known from Fig. 6: under normal temperature, the maximum adsorption capacity of HMIMs and HNIMs to tsiklomitsin is respectively 20.15 μm of olg
-1with 12.10 μm of olg
-1, demonstrate good selective adsorption effect, simultaneously, adsorption test data meet Freundlich Isothermal Model well,
The kinetics matched curve of Fig. 7 HMIMs and HNIMs tetracycline adsorption.As can be seen from Figure 7: adsorption equilibrium reaches very soon, experimental data matching pseudo-second order kinetic equation well.In whole time range, HMIMs is greater than the adsorptive capacity of HNIMs to the adsorptive capacity of tsiklomitsin, shows good specific recognition performance, and the avtive spot existing in imprinted polymer and match with tetracycline molecule is described.
Fig. 8 imprinted polymer and non-imprinted polymer are to the adsorption selectivity of tsiklomitsin.As can be known from Fig. 8: the adsorptive capacity of imprinted polymer to tsiklomitsin is maximum, good Selective recognition and absorption property has been shown.
Embodiment
1, below in conjunction with concrete embodiment, the present invention will be further described:
According to tsiklomitsin (TC): methacrylic acid (MAA): trimethylolpropane trimethacrylate (TMPTMA): the mol ratio of vinylbenzene (St) is the ratio of 1:3:24:40 (mmol/mmol/mmol/mmol), adds tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate successively in round-bottomed flask.According to vinylbenzene: the mass ratio of ethanol is the ratio of 1:50 (g/g), adds ethanol, ultrasonic disperse in flask, form homogeneous phase solution.Under room temperature, pre-assembled 12 hours of lucifuge; Ultrasonic degas, logical nitrogen 20min, according to Diisopropyl azodicarboxylate (AIBN): the mass ratio of ethanol is the ratio of 0.02:100 (g/g), Diisopropyl azodicarboxylate is added as initiator in solution, flask is placed in water bath with thermostatic control vibrator, rotating speed is from 25 in 100r/min, 1.0h
oc is warming up to 60
oc, precipitation polymerization reaction 12h; According to hydroxyethyl methylacrylate (HEMA): the mass ratio of ethanol is the ratio of 0.01:100 (g/g), adds hydroxyethyl methylacrylate, 60 in system
oc continues oscillatory reaction 12h.After reaction terminates, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; Be the methyl alcohol of 9:1 by volume ratio: acetic acid mixture surname extraction 6h, repeatedly, eluted template molecule, to elutriant ultraviolet-visible pectrophotometer can't detect tsiklomitsin, with ethanol and distilled water by product washing to neutral, 60
ounder C, vacuum-drying is to constant weight, obtains hydrophilic molecular engram polymer microballoon (HMIMs).Take same preparation method, but do not add tsiklomitsin in process as template molecule, obtain the non-imprinted polymer microballoon (HNIMs) of wetting ability.If in polymerization process, do not add hydroxyethyl methylacrylate and participate in polymerization, obtain molecular blotting polymer microsphere (MIMs); If not methylate Hydroxyethyl acrylate and tsiklomitsin, obtain non-imprinted polymer microballoon (NIMs).
2, below in conjunction with concrete embodiment, the present invention will be further described:
According to tsiklomitsin (TC): methacrylic acid (MAA): trimethylolpropane trimethacrylate (TMPTMA): the mol ratio of vinylbenzene (St) is the ratio of 1:6:48:50 (mmol/mmol/mmol/mmol), adds tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate successively in round-bottomed flask.According to vinylbenzene: the mass ratio of ethanol is the ratio of 1:100 (g/g), adds ethanol, ultrasonic disperse in flask, form homogeneous phase solution.Under room temperature, the pre-assembled 12-24 hour of lucifuge; Ultrasonic degas, logical nitrogen 30min, according to Diisopropyl azodicarboxylate (AIBN): the mass ratio of ethanol is the ratio of 0.04:100 (g/g), Diisopropyl azodicarboxylate is added as initiator in solution, flask is placed in water bath with thermostatic control vibrator, rotating speed is from 25 in 200r/min, 1.0h
oc is warming up to 60
oc, precipitation polymerization reaction 12h; According to hydroxyethyl methylacrylate (HEMA): the mass ratio of ethanol is the ratio of 0.03:100 (g/g), adds hydroxyethyl methylacrylate, 60 in system
oc continues oscillatory reaction 12h.After reaction terminates, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; Be the methyl alcohol of 9:1 by volume ratio: acetic acid mixture surname extraction 6h, repeatedly, eluted template molecule, to elutriant ultraviolet-visible pectrophotometer can't detect tsiklomitsin, with ethanol and distilled water by product washing to neutral, 60
ounder C, vacuum-drying is to constant weight, obtains hydrophilic molecular engram polymer microballoon (HMIMs).Take same preparation method, but do not add tsiklomitsin in process as template molecule, obtain the non-imprinted polymer microballoon (HNIMs) of wetting ability.If in polymerization process, do not add hydroxyethyl methylacrylate and participate in polymerization, obtain molecular blotting polymer microsphere (MIMs); If not methylate Hydroxyethyl acrylate and tsiklomitsin, obtain non-imprinted polymer microballoon (NIMs).
2, below in conjunction with concrete embodiment, the present invention will be further described:
In the present invention, in specific embodiments, absorption property evaluation is carried out by the following method: utilize Staticadsorption experiment to complete.Certain density for 10ml tetracycline is joined in centrifuge tube, respectively to wherein adding 10mgHMIMs and HNIMs, being placed in water bath with thermostatic control and leaving standstill 12h, investigate solution ph, time of repose, temperature to the impact of adsorbent tetracycline molecule.After absorption, by collected by centrifugation, obtain clear liquid at the middle and upper levels, the tetracycline molecule concentration uv-vis spectra do not adsorbed records, and according to result calculate loading capacity (
q e, μm ol/g).
Wherein
c 0(μm ol/L) and
c e(μm ol/L) is the concentration of tsiklomitsin before and after absorption respectively,
wg () is adsorbent amount,
v(mL) be test fluid volume.
Experiment examination example 1: get 10mgHMIMs and HNIMs respectively and join in the centrifuge tube of 10ml, then getting the tetracycline that 10ml starting point concentration is respectively 10,30,50,80,100,120,150,180 μm of ol/L respectively joins in centrifuge tube, centrifuge tube is placed in the water-bath of three differing tempss (298K, 308K and 318K) and leaves standstill 12.0h.After absorption, collected by centrifugation supernatant liquid, is not measured by the tetracycline molecule concentration ultraviolet-visible pectrophotometer adsorbed, and calculates loading capacity.Fig. 6 result shows: along with the rising of temperature and concentration, adsorptive capacity increases gradually, finally reaches adsorption equilibrium, and wetting ability imprinted polymer is greater than the non-imprinted polymer of wetting ability all the time to the adsorptive capacity of tsiklomitsin, proves to there is a large amount of trace holes.
Experiment examination example 2: getting 10ml starting point concentration is that the tetracycline of 80 μm of ol/L joins in centrifuge tube, add 10mgHMIMs and HNIMs respectively, centrifuge tube is placed in the water-bath of 298K and leaves standstill 10,20,30,45,60,90,120,150,180 and 240 minutes respectively.After having left standstill, collected by centrifugation supernatant liquid, is not measured by the tetracycline molecule concentration ultraviolet-visible pectrophotometer adsorbed, and calculates loading capacity according to result.Fig. 7 result shows: HMIMs and HNIMs have good kinetics of adsorption performance to Fourth Ring, substantially reaches adsorption equilibrium in 3.0h.
Experiment examination example 3: select duomycin, Cephalexin Monohydrate Micro/Compacted and Ciprofloxacin to be the antibiotic compound of competitive adsorption.Configuring solubility is respectively 100 μm of above-mentioned three kinds of microbiotic of ol/L.Getting the solution that 10ml prepares joins in centrifuge tube, adds 10mgHMIMs and HNIMs respectively, centrifuge tube is placed in the water-bath of 298K and leaves standstill 12h respectively.After absorption, collected by centrifugation supernatant liquid, is not measured by the various competitive adsorption antibiotic concentration ultraviolet-visible pectrophotometers adsorbed.Fig. 8 result shows, wetting ability imprinted polymer has significant specific recognition to tsiklomitsin, and loading capacity is apparently higher than other microbiotic.
Claims (1)
1. the alternative synthetic method identifying the hydrophilic polymer microballoon of tsiklomitsin, is characterized in that carrying out according to following step:
Tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate is added in round-bottomed flask; In flask, add ethanol, ultrasonic disperse, form homogeneous phase solution;
Under room temperature, the pre-assembled 12-24 hour of lucifuge; Ultrasonic degas, logical nitrogen 20-30min, adds Diisopropyl azodicarboxylate as initiator, flask is placed in water bath with thermostatic control vibrator in solution, and rotating speed is be warming up to 60 DEG C from 25 DEG C in 100-200r/min, 1.0h, precipitation polymerization reaction 12h; In system, add hydroxyethyl methylacrylate, 60 DEG C are continued oscillatory reaction 12h; After reaction terminates, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; Be the methyl alcohol of 9:1 by volume ratio: acetic acid mixture surname extraction 6.0h, repeatedly, eluted template molecule, to elutriant ultraviolet-visible pectrophotometer can't detect tsiklomitsin, with ethanol and distilled water, product is washed to neutral, at 60 DEG C, vacuum-drying is to constant weight, obtains hydrophilic molecular engram polymer microballoon;
Tsiklomitsin in step: methacrylic acid: trimethylolpropane trimethacrylate: the mol ratio of vinylbenzene (St) is 1:(3-6): (24-48): (40-50); Vinylbenzene: the mass ratio of ethanol is 1:(50-100); Diisopropyl azodicarboxylate: the mass ratio of ethanol is (0.02-0.04): 100; Hydroxyethyl methylacrylate: the mass ratio of ethanol is (0.01-0.03): 100.
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| CN107913682A (en) * | 2017-11-08 | 2018-04-17 | 常州大学 | A kind of method for preparing porous temperature sensitive molecular imprinting adsorbing agent |
| CN109012587B (en) * | 2018-08-21 | 2021-03-23 | 齐鲁工业大学 | Preparation method of tetracycline hydrophilic carbon composite adsorbent |
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| CN102059104A (en) * | 2009-11-17 | 2011-05-18 | 南开大学 | Surface-hydrophilic molecularly imprinted polymer microsphere and preparation method thereof |
| CN102952236A (en) * | 2011-08-29 | 2013-03-06 | 南开大学 | Molecularly imprinted polymeric microsphere resin applicable to aqueous solution system and preparing method thereof |
| CN103304723A (en) * | 2013-07-01 | 2013-09-18 | 江苏大学 | Green preparation method of hydrophilic molecular engram polymer |
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