CN102603972B - Preparation method of dimethyl methylphosphonate (DMMP) molecular imprinting polymer microspheres - Google Patents
Preparation method of dimethyl methylphosphonate (DMMP) molecular imprinting polymer microspheres Download PDFInfo
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Abstract
The invention relates to a preparation method of a molecular imprinting polymer. The preparation method comprises the following steps: dissolving dimethyl methylphosphonate (DMMP), a functional monomer A and a functional monomer B in a pore former, performing ultrasonic degassing for at least 5 minutes, placing the mixture in a refrigerator for above 8 hours to obtain a template molecule-monomer complex, adding a crosslinking agent in the template molecule-monomer complex, performing ultrasonic vibration for at least 30 minutes, introducing nitrogen for at least 15 minutes while adding an initiator, sealing, performing thermal polymerization in a suspension prepared from polyvinyl alcohol, cooling to the room temperature to separate out precipitates, centrifuging, performing Soxhlet extraction on the obtained polymer to ensure that the polymer has no imprinted molecules, washing microspheres with chloroform to remove residual methanol and acetic acid, and drying the microspheres in vacuum to reach a constant weight and obtain DMMP molecular imprinting polymer microspheres. The DMMP molecular imprinting polymer microspheres prepared by the method have the advantages of obviously higher adsorption capacity, larger specific surface area and good selectivity.
Description
Technical field
The present invention relates to a kind of technical field of bioengineering, be specifically related to a kind of preparation method of molecularly imprinted polymer.
Background technology
Organophosphorus pesticide is current most popular chemical pesticide, and this agricultural chemicals lethality is strong, is difficult to protection, is the study hotspot that chemistry is detected field always.Organophosphorus insecticide remaining in environment forms the phosphorylated Pseudocholinesterase with Pseudocholinesterase in vivo, makes cholinesterase activity suppressed, causes nervous dysfunction, even occurs dead.Dimethyl methyl phosphonate (dimethyl methyl phosphonate, DMMP) belong to the simulant of organophosphorus pesticide, it has, the characteristics such as toxicity little, operational safety similar to the organophosphorus pesticide molecular structure, and contain to organophosphorus toxicants detect very important-P=O ,-the P-O-key, it is furtherd investigate, reference and foundation can be provided for the method for setting up effective detection organophosphorus toxicants.
The detection method of dimethyl methyl phosphonate (DMMP) mainly contains vapor-phase chromatography, liquid phase chromatography, sensor method etc. at present.Usually vapor-phase chromatography, these methods of liquid phase chromatography all exist sample pre-treatments loaded down with trivial details, the difficulty such as take time and effort.And, for sensor method, normally select the material of dimethyl methyl phosphonate sensitivity is made to sensor, this method not only needs to screen the design requirements that can meet some special sensor and performer, and complex operation, is difficult for promoting.Polymkeric substance prepared by molecular imprinting, as the material of Solid-Phase Extraction, can reach very high selectivity and sensitivity, realizes target compound is carried out to sharp separation, detection.
Although molecular imprinting has obtained application more widely at present, in actual the use, still there are many problems.Mainly that current function monomer is used and select larger limitation and blindness, cause in molecular imprinting the binding site of template molecule and function monomer limited, in use, adsorptive capacity is very low for the molecularly imprinted polymer of preparing, and is difficult to carry out the trace detection to template molecule.
Existing technical literature retrieval is found, not yet found so far the relevant report with the present invention's special topic dimethyl methyl phosphonate (DMMP) imprinted polymer.
Summary of the invention
Technical problem to be solved by this invention just is to provide a kind of preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere, it is by selecting specific function monomer, the molecularly imprinted polymer of preparing is large to the adsorptive capacity of the simulant dimethyl methyl phosphonate of machine phosphorus insecticide, is easy to detect and separate dimethyl methyl phosphonate.
Technical problem to be solved by this invention is to realize by such technical scheme, and it comprises the following steps:
Step 1, be dissolved in dimethyl methyl phosphonate, function monomer A and function monomer B in pore-creating agent, and ultrasonic degas is at least 5min, be put in standingly in refrigerator more than 8 hours, to obtain template molecule-monomer complex, wherein:
The mol ratio of a, dimethyl methyl phosphonate, function monomer A, function monomer B is 1:4:0 ~ 1,
B, pore-creating agent are 1:5 ~ 15 with reactant cumulative volume ratio,
C, function monomer A are a kind of in methacrylic acid MAA, vinylformic acid (AA), trifluoromethyl acrylate (TFMAA), methyl methacrylate (MMA), 4-vinylpyridine (4-VP), 2-vinyl pyridine (2-VP), acrylamide,
D, function monomer B is a kind of metalloporphyrin, described metalloporphyrin has 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl gadolinium porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl zinc protoporphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl cobalt porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl manganoporphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl iron porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl copper porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl nickel-porphyrin,
Step 2, linking agent is joined in template molecule-monomer complex that step 1 prepares gained, sonic oscillation, time is no less than 30min, passes at least 15min of nitrogen, adds initiator simultaneously, sealing, thermopolymerization in the suspension made from polyvinyl alcohol, the thermopolymerization temperature is that 60 ~ 75 ℃, time are 20 ~ 30h, wherein:
F, template molecule, linking agent, initiator mol ratio are 1:20:0.24 ~ 0.4,
G, linking agent are linking agent commonly used in current molecular imprinting preparation, comprise ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TRIM), divinylbenzene (DVB) or N, N '-methylene-bisacrylamide,
H, initiator are Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide (BPO),
I, polyvinyl alcohol liquid concentration are 1.3% ~ 4%;
Step 3, be cooled to room temperature, and Precipitation is arranged, centrifugal, and the resulting polymers Soxhlet is extracted into without microsphere, and it is methyl alcohol/acetic acid 9/1(V/V that Soxhlet is extracted organic solvent used), extraction time is at least 24h;
Step 4, continue the washing microballoon with chloroform, removes residual methanol and acetic acid, puts into the vacuum-drying that temperature is 50 ~ 80 ℃, and vacuum-drying, to constant weight, obtains the molecular blotting polymer microsphere of dimethyl methyl phosphonate (DMMP).
Adopting the present invention to take organophosphorus pesticide aids drug dimethyl methyl phosphonate (DMMP) is template molecule, prepared two quasi-molecule imprinted polymers: a class is for using the molecular blotting polymer microsphere of simple function monomer, and the another kind of molecular engram microsphere prepared for the mixing functions monomer that contains metalloporphyrin.Use the microballoon of simple function monomer, surface is relatively smooth, and a small amount of adsorptive capacity is arranged, by comparison, be added with the microballoon of the mixing functions monomer of metalloporphyrin, adsorptive capacity significantly improves, specific surface area increases, selectivity is good, median size is 20-50 μ m, on the molecular blotting polymer microsphere surface, a lot of apertures are arranged, can off-line or online and ultraviolet-visible pectrophotometer, liquid chromatographies etc. are analyzed Instrument crosslinking, dimethyl methyl phosphonate in environmental sample is carried out to separating-purifying, also can be used as the filler of Solid-Phase Extraction and liquid-phase chromatographic column, the separation of realization to dimethyl methyl phosphonate, enrichment and purifying, simultaneously can be to reference the method, the metalloporphyrin peripheral structure is modified, increased the binding site of function monomer and template molecule, improved the accuracy of trace detection.
The accompanying drawing explanation
Accompanying drawing of the present invention is described as follows:
Fig. 1 is for take the scanning electron microscope (SEM) photograph of the DMMP microballoon that MAA is function monomer;
Fig. 2 is for take the scanning electron microscope (SEM) photograph of the DMMP microballoon that zinc protoporphyrin and MAA be function monomer;
Fig. 3 is for take the scanning electron microscope (SEM) photograph of the DMMP microballoon that gadolinium porphyrin and MAA be function monomer.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
Get dimethyl methyl phosphonate (DMMP) 1mmol, methacrylic acid (MAA) 4mmol, be dissolved in the 20ml chloroformic solution, sonic oscillation 10min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent ethylene glycol dimethacrylate (EGDMA) and join in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2After 15min, add 0.3mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing, in 60 ℃ of water-soluble thermopolymerization 24h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with the chloroform washing, put into 50 ℃ of vacuum chambers and be dried to constant weight subsequently, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m, its invention effect as shown in Figure 1, this polymer microballoon surface is relatively smooth, and the maximal absorptive capacity that is to DMMP is 400 μ mmol/g, and the high specific surface-area is 235.20m
2/ g.
In the following example, the synthetic preparation of metalloporphyrin belongs to the category of prior art, can be referring to document " molecularly imprinted polymer based on metalloporphyrin synthetic and to the research of triazole bactericidal agent recognition performance " (polymer journal the 8th phase 809-813 page, in August, 2009).The preparation of metalloporphyrin is all with the 5-(4-hydroxy phenyl)-10, 15, the 20-Triphenylporphyrin is raw material, only the reaction times is adjusted, and different eluents is purified according to metal polarity different choice, can make 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl gadolinium porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl zinc protoporphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl cobalt porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl manganoporphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl iron porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl copper porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl nickel-porphyrin.
Embodiment 2
Get dimethyl methyl phosphonate (DMMP) 1mmol, vinylformic acid (MAA) 4mmol, and zinc protoporphyrin 1mmol, be dissolved in the 20ml chloroformic solution, sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent trimethylolpropane trimethacrylate (TRIM) and join in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2After 15min, add 0.4mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing, in 60 ℃ of water-soluble thermopolymerization 28h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 75 ℃ of vacuum chambers and be dried to constant weight, final obtain the molecule that median size is 20-50 μ m and print polymkeric substance, its invention effect as shown in Figure 2, this polymer microballoon surface irregularity, specific surface area is large, aperture is even, and the maximal absorptive capacity that is to DMMP is 950 μ mmol/g, and the high specific surface-area is 430.30m
2/ g.
Embodiment 3
Get dimethyl methyl phosphonate (DMMP) 1mmol, methyl methacrylate (MMA) 4mmol, and gadolinium porphyrin 0.3mmol, be dissolved in the 10ml chloroformic solution, sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent ethylene glycol dimethacrylate (EGDMA) and join in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2after 15min, add 0.28mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing, in 70 ℃ of water-soluble thermopolymerization 24h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 70 ℃ of vacuum chambers and be dried to constant weight, the molecule that final acquisition median size is 20-50 μ m prints polymkeric substance, its invention effect as shown in Figure 3, this polymer microballoon surface irregularity, specific surface area is large, aperture is even, the maximal absorptive capacity that is to DMMP is 610 μ mmol/g, the high specific surface-area is 400.60m
2/ g.
Embodiment 4
Get dimethyl methyl phosphonate (DMMP) 1mmol, trifluoromethyl acrylate (TFMAA) 4mmol, and cobalt porphyrin 0.5 mmol, be dissolved in the 15ml chloroformic solution, sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent ethylene glycol dimethacrylate (EGDMA) and join in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2After 15min, add 0.25mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing, in 60 ℃ of water-soluble thermopolymerization 24h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 60 ℃ of vacuum chambers and be dried to constant weight, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m, this polymer microballoon surface irregularity, the maximal absorptive capacity that is to DMMP is 768 μ mmol/g, and the high specific surface-area is 428.60m
2/ g.
Embodiment 5
Get dimethyl methyl phosphonate (DMMP) 1mmol, 4-vinylpyridine (4-VP) 4mmol, and synthetic iron porphyrin 0.7 mmol, be dissolved in the 30ml chloroformic solution, sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent divinylbenzene (DVB) and join in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2After 15min, add 0.24mmol initiator benzoyl peroxide (BPO), sealing, in 62 ℃ of water-soluble thermopolymerization 20h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 65 ℃ of vacuum chambers and be dried to constant weight, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m, this polymer microballoon surface irregularity, the maximal absorptive capacity that is to DMMP is 852 μ mmol/g, and the high specific surface-area is 415.40m
2/ g.
Embodiment 6
Get dimethyl methyl phosphonate (DMMP) 1mmol, 2-vinyl pyridine (2-VP) 4mmol, and synthetic copper porphyrin 0.1 mmol, be dissolved in the 30ml chloroformic solution, sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent divinylbenzene (DVB) and join in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2After 15min, add 0.3mmol initiator benzoyl peroxide (BPO), sealing, in 65 ℃ of water-soluble thermopolymerization 20h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 75 ℃ of vacuum chambers and be dried to constant weight, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m, this polymer microballoon surface irregularity, the maximal absorptive capacity that is to DMMP is 532 μ mmol/g, and the high specific surface-area is 387.63m
2/ g.
Embodiment 7
Get dimethyl methyl phosphonate (DMMP) 1mmol, acrylamide 4mmol, and synthetic nickel-porphyrin 0.4 mmol, be dissolved in the 20ml chloroformic solution sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent N, N '-methylene-bisacrylamide joins in the template molecule-monomer complex for preparing gained, ultrasonic degas 30min, at least pass into N
2After 15min, add 0.4mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing, in 60 ℃ of water-soluble thermopolymerization 20h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 55 ℃ of vacuum chambers and be dried to constant weight, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m, this polymer microballoon surface irregularity, the maximal absorptive capacity that is to DMMP is 715 μ mmol/g, and the high specific surface-area is 425.30m
2/ g.
Embodiment 8
Get dimethyl methyl phosphonate (DMMP) 1mmol, acrylamide 4mmol, and synthetic manganoporphyrin 0.6 mmol, be dissolved in the 30ml chloroformic solution sonic oscillation 5min, be put in refrigerator interior standing 8 hours, form template molecule-monomer complex, take 20mmol linking agent N, N '-methylene-bisacrylamide joins in the template molecule-monomer complex for preparing gained, sonic oscillation 30min, at least pass into N
2After 15min, add 0.3mmol initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), sealing, in 68 ℃ of water-soluble thermopolymerization 27h, taking-up is cooled to room temperature, centrifugal, methyl alcohol for resulting polymers/acetic acid 9/1(V/V) be washed till without microsphere, with chloroform, wash subsequently, put into 80 ℃ of vacuum chambers and be dried to constant weight, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m, this polymer microballoon surface irregularity, the maximal absorptive capacity that is to DMMP is 784 μ mmol/g, and the high specific surface-area is 421.35m
2/ g.
Claims (4)
1. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere comprises the following steps:
Step 1, be dissolved in dimethyl methyl phosphonate, function monomer A and function monomer B in pore-creating agent, and ultrasonic degas is at least 5min, be put in standingly in refrigerator more than 8 hours, to obtain template molecule-monomer complex, wherein:
The mol ratio of a, dimethyl methyl phosphonate, function monomer A, function monomer B is 1:4:0 ~ 1,
B, pore-creating agent are 1:5 ~ 15 with reactant cumulative volume ratio,
C, function monomer A are a kind of in methacrylic acid MAA, vinylformic acid (AA), trifluoromethyl acrylate (TFMAA), methyl methacrylate (MMA), 4-vinylpyridine (4-VP), 2-vinyl pyridine (2-VP), acrylamide,
D, function monomer B is a kind of metalloporphyrin, described metalloporphyrin has 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl gadolinium porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl zinc protoporphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl cobalt porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl manganoporphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl iron porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl copper porphyrin, 5-(4-methacryloxypropyl phenyl)-10, 15, 20-triphenyl nickel-porphyrin,
E, pore-creating agent are chloroform or methylene dichloride;
Step 2, linking agent is joined in template molecule-monomer complex that step 1 prepares gained, sonic oscillation, time is no less than 30min, passes at least 15min of nitrogen, adds initiator simultaneously, sealing, thermopolymerization in the suspension made from polyvinyl alcohol, the thermopolymerization temperature is that 60 ~ 75 ℃, time are 20 ~ 30h, wherein:
F, template molecule, linking agent, initiator mol ratio are 1:20:0.24 ~ 0.4,
G, linking agent are linking agent commonly used in current molecular imprinting preparation, comprise ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TRIM), divinylbenzene (DVB) or N, N '-methylene-bisacrylamide,
H, initiator are Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide (BPO),
I, polyvinyl alcohol liquid concentration are 1.3% ~ 4%;
Step 3, be cooled to room temperature, and Precipitation is arranged, centrifugal, and the resulting polymers Soxhlet is extracted into without microsphere, and it is methyl alcohol/acetic acid 9/1(V/V that Soxhlet is extracted organic solvent used), extraction time is at least 24h;
Step 4, continue the washing microballoon with chloroform, removes residual methanol and acetic acid, puts into the vacuum-drying that temperature is 50 ~ 80 ℃, and vacuum-drying, to constant weight, obtains the molecular blotting polymer microsphere of dimethyl methyl phosphonate (DMMP).
2. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere according to claim 1, it is characterized in that: in described step 1, the mol ratio of dimethyl methyl phosphonate, function monomer A, function monomer B is 1:4:1, and pore-creating agent and reactant cumulative volume are than being 1:7.5.
3. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere according to claim 1, it is characterized in that: in described step 2, template molecule, linking agent, initiator mol ratio are 1:20:0.3.
4. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere according to claim 1, it is characterized in that: the median size of the molecular blotting polymer microsphere of described dimethyl methyl phosphonate (DMMP) is 20-50 μ m.
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