CN102603972A - 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 present most popular chemical pesticide, and this agricultural chemicals lethality is strong, is difficult to protection, is that chemistry is detected hot research fields always.Organophosphorus insecticide remaining in the environment forms the phosphorylated Pseudocholinesterase with Pseudocholinesterase in vivo, and cholinesterase activity is suppressed, and causes nervous dysfunction, even occurs dead.Dimethyl methyl phosphonate (dimethyl methyl phosphonate; DMMP) belong to the simulant of organophosphorus pesticide; It has characteristics such as, operational safety little with organophosphorus pesticide similar molecular, toxicity; 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, difficulty such as take time and effort.And for sensor method, normally select the responsive material of dimethyl methyl phosphonate is processed transmitter, this method not only need be screened the design requirements that can satisfy some special sensor and performer, and complex operation, is difficult for promoting.With the polymkeric substance of molecular imprinting preparation material as SPE, then can reach very high selectivity and sensitivity, realize target compound is carried out sharp separation, detection.
Though molecular imprinting has obtained using more widely at present, still there are many problems in actual the use.Mainly be that present function monomer uses and selects bigger limitation and blindness are all arranged; Cause in the molecular imprinting binding site of template molecule and function monomer limited; The molecularly imprinted polymer of preparing in use, adsorptive capacity is very low, is difficult to carry out the trace detection to template molecule.
Existing TP retrieval is found, do not found relevant report so far as yet 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 provides a kind of preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere; It is through selecting the particular functionality monomer; The molecularly imprinted polymer of preparing is big 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 that through such technical scheme it may further comprise the steps:
Step 1 is dissolved in dimethyl methyl phosphonate, function monomer A and function monomer B in the pore-creating agent, and ultrasonic degas is at least 5min, is put in to leave standstill in the refrigerator more than 8 hours, obtains 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 TV ratio,
C, function monomer A are a kind of in methylacrylic acid MAA, vinylformic acid (AA), trifluoromethyl acrylate (TFMAA), methacrylic ester (MMA), 4-vinylpyridine (4-VP), 2-vinyl pyridine (2-VP), the acrylic amide,
D, function monomer B are a kind of metalloporphyrin, and 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 joins linking agent in the template molecule-monomer complex of step 1 preparation gained sonic oscillation; Time is no less than 30min, feeds nitrogen 15min at least, adds initiator simultaneously; Sealing; Thermopolymerization in the suspension-s of processing with Z 150PH, thermopolymerization temperature are 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 the present molecular imprinting preparation, comprise ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TRIM), divinylbenzene (DVB) or N, N '-methylene-bisacrylamide,
H, initiator are Diisopropyl azodicarboxylate (AIBN), AMBN or Lucidol (BPO),
I, Z 150PH liquid concentration are 1.3% ~ 4%;
Step 3 is cooled to room temperature, has deposition to separate out, and centrifugal, resulting polymers Suo Shi is extracted into no microsphere, and it is methyl alcohol/acetic acid 9/1 (V/V) that Suo Shi extracts used organic solvent, and extraction time is at least 24h;
Step 4 continues the washing microballoon with chloroform, removes residual methanol and acetic acid, puts into temperature and be 50 ~ 80 ℃ vacuum-drying, and vacuum-drying obtains the molecular blotting polymer microsphere of dimethyl methyl phosphonate (DMMP) to constant weight.
Adopting the present invention is template molecule with organophosphorus pesticide aids drug dimethyl methyl phosphonate (DMMP); Prepared two quasi-molecule imprinted polymers: one type for using the monomeric molecular blotting polymer microsphere of simple function, and another kind of molecular engram microsphere for the mixing functions monomer preparation that contains metalloporphyrin.Use the monomeric microballoon of simple function, the surface is smooth relatively, and a spot of adsorptive capacity is arranged; By comparison, be added with the monomeric microballoon of mixing functions of metalloporphyrin, adsorptive capacity significantly improves; Specific surface area increases, and selectivity is good, and 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 chromatography etc. analyze Instrument crosslinking, the dimethyl methyl phosphonate in the environmental sample is separated purification; Also can be used as the filler of SPE and liquid-phase chromatographic column; Realization can be modified the metalloporphyrin peripheral structure with reference to this method separation, enrichment and the purifying of dimethyl methyl phosphonate simultaneously; Increase the binding site of function monomer and template molecule, improved the accuracy of trace detection.
Description of drawings
Description of drawings of the present invention is following:
Fig. 1 is for being the sem photograph of the DMMP microballoon of function monomer with MAA;
Fig. 2 is for being the sem photograph of the DMMP microballoon of function monomer with zinc protoporphyrin and MAA;
Fig. 3 is for being the sem photograph of the DMMP microballoon of function monomer with gadolinium porphyrin and MAA.
Embodiment
Below in conjunction with embodiment the present invention is described further:
Embodiment 1
Get dimethyl methyl phosphonate (DMMP) 1mmol, methylacrylic acid (MAA) 4mmol is dissolved in the 20ml chloroformic solution; Sonic oscillation 10min; Be put in and leave standstill 8 hours in the refrigerator, form template molecule-monomer complex, take by weighing 20mmol linking agent ethylene glycol dimethacrylate (EGDMA) and join in the template molecule-monomer complex of preparation gained; Ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.3mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing; In 60 ℃ of water-soluble thermopolymerization 24h, take out and be cooled to room temperature, centrifugal; Resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V), with the chloroform washing, puts into vacuum chamber and is dried to constant weight for 50 ℃ subsequently; The molecule seal polymkeric substance that final acquisition median size is 20-50 μ m, its invention effect is as shown in Figure 1, and this polymer microballoon surface is smooth relatively; 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 " based on the synthetic of the molecularly imprinted polymer of metalloporphyrin and to the research of triazole bactericidal agent recognition performance " (the 8th phase of polymer journal 809-813 page or leaf, in August, 2009).The preparation of metalloporphyrin all is that 20-triphenyl porphyrin is a raw material, only the reaction times is adjusted with 5-(4-hydroxy phenyl)-10,15; And the eluent purification different 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 is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex; Take by weighing 20mmol linking agent trimethylolpropane trimethacrylate (TRIM) and join in the template molecule-monomer complex of preparation gained, ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.4mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing is in 60 ℃ of water-soluble thermopolymerization 28h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 75 ℃ subsequently, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m; Its invention effect is as shown in Figure 2, this polymer microballoon surface irregularity, and specific surface area is big; The 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, methacrylic ester (MMA) 4mmol, and gadolinium porphyrin 0.3mmol; Be dissolved in the 10ml chloroformic solution, sonic oscillation 5min is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex; Take by weighing 20mmol linking agent ethylene glycol dimethacrylate (EGDMA) and join in the template molecule-monomer complex of preparation gained, ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.28mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing is in 70 ℃ of water-soluble thermopolymerization 24h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 70 ℃ subsequently, finally obtaining median size is the molecule seal polymkeric substance of 20-50 μ m; Its invention effect is as shown in Figure 3, this polymer microballoon surface irregularity, and specific surface area is big; The aperture is even, and the maximal absorptive capacity that is to DMMP is 610 μ mmol/g, and 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 is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex; Take by weighing 20mmol linking agent ethylene glycol dimethacrylate (EGDMA) and join in the template molecule-monomer complex of preparation gained, ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.25mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing is in 60 ℃ of water-soluble thermopolymerization 24h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 60 ℃ subsequently, 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, 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 is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex; Take by weighing 20mmol linking agent divinylbenzene (DVB) and join in the template molecule-monomer complex of preparation gained, ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.24mmol initiator Lucidol (BPO), sealing is in 62 ℃ of water-soluble thermopolymerization 20h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 65 ℃ subsequently, 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, 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 is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex; Take by weighing 20mmol linking agent divinylbenzene (DVB) and join in the template molecule-monomer complex of preparation gained, ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.3mmol initiator Lucidol (BPO), sealing is in 65 ℃ of water-soluble thermopolymerization 20h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 75 ℃ subsequently, 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, the high specific surface-area is 387.63m
2/ g.
Embodiment 7
Get dimethyl methyl phosphonate (DMMP) 1mmol, acrylic amide 4mmol, and synthetic nickel-porphyrin 0.4 mmol; Be dissolved in the 20ml chloroformic solution, sonic oscillation 5min is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex, take by weighing 20mmol linking agent N, N '-methylene-bisacrylamide joins in the template molecule-monomer complex of preparation gained; Ultrasonic degas 30min feeds N at least
2Behind the 15min, add 0.4mmol initiator Diisopropyl azodicarboxylate (AIBN), sealing is in 60 ℃ of water-soluble thermopolymerization 20h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 55 ℃ subsequently, 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, the high specific surface-area is 425.30m
2/ g.
Embodiment 8
Get dimethyl methyl phosphonate (DMMP) 1mmol, acrylic amide 4mmol, and synthetic manganoporphyrin 0.6 mmol; Be dissolved in the 30ml chloroformic solution, sonic oscillation 5min is put in and leaves standstill 8 hours in the refrigerator; Form template molecule-monomer complex, take by weighing 20mmol linking agent N, N '-methylene-bisacrylamide joins in the template molecule-monomer complex of preparation gained; Sonic oscillation 30min feeds N at least
2Behind the 15min, add 0.3mmol initiator AMBN, sealing is in 68 ℃ of water-soluble thermopolymerization 27h; Taking-up is cooled to room temperature, and is centrifugal, and resulting polymers is washed till no microsphere with methyl alcohol/acetic acid 9/1 (V/V); With the chloroform washing, put into vacuum chamber and be dried to constant weight for 80 ℃ subsequently, 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, the high specific surface-area is 421.35m
2/ g.
Claims (4)
1. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere may further comprise the steps:
Step 1 is dissolved in dimethyl methyl phosphonate, function monomer A and function monomer B in the pore-creating agent, and ultrasonic degas is at least 5min, is put in to leave standstill in the refrigerator more than 8 hours, obtains 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 TV ratio,
C, function monomer A are a kind of in methylacrylic acid MAA, vinylformic acid (AA), trifluoromethyl acrylate (TFMAA), methacrylic ester (MMA), 4-vinylpyridine (4-VP), 2-vinyl pyridine (2-VP), the acrylic amide,
D, function monomer B are a kind of metalloporphyrin, and 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 joins linking agent in the template molecule-monomer complex of step 1 preparation gained sonic oscillation; Time is no less than 30min, feeds nitrogen 15min at least, adds initiator simultaneously; Sealing; Thermopolymerization in the suspension-s of processing with Z 150PH, thermopolymerization temperature are 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 the present molecular imprinting preparation, comprise ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TRIM), divinylbenzene (DVB) or N, N '-methylene-bisacrylamide,
H, initiator are Diisopropyl azodicarboxylate (AIBN), AMBN or Lucidol (BPO),
I, Z 150PH liquid concentration are 1.3% ~ 4%;
Step 3 is cooled to room temperature, has deposition to separate out, and centrifugal, resulting polymers Suo Shi is extracted into no microsphere, and it is methyl alcohol/acetic acid 9/1 (V/V) that Suo Shi extracts used organic solvent, and extraction time is at least 24h;
Step 4 continues the washing microballoon with chloroform, removes residual methanol and acetic acid, puts into temperature and be 50 ~ 80 ℃ vacuum-drying, and vacuum-drying obtains the molecular blotting polymer microsphere of dimethyl methyl phosphonate (DMMP) to constant weight.
2. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere according to claim 1; It is characterized in that: in the said 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 TV are than being 1:7.5.
3. the preparation method of dimethyl methyl phosphonate molecular blotting polymer microsphere according to claim 1 is characterized in that: in the said 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 is characterized in that: the median size of the molecular blotting polymer microsphere of said dimethyl methyl phosphonate (DMMP) is 20-50 μ m.
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| CN102977403A (en) * | 2012-12-24 | 2013-03-20 | 重庆大学 | Molecularly imprinted membrane based on porphyrin and acrylic monomers for organophosphorus pesticide and application thereof |
| CN103172899A (en) * | 2012-12-24 | 2013-06-26 | 重庆大学 | Molecular imprinting composite membrane for organophosphorus pesticide detection and application of membrane |
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| CN101113955A (en) * | 2007-08-28 | 2008-01-30 | 重庆大学 | Material for detecting micro-trace dimethyl methyl phosphomate and method for making same |
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| CN101113955A (en) * | 2007-08-28 | 2008-01-30 | 重庆大学 | Material for detecting micro-trace dimethyl methyl phosphomate and method for making same |
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| CN103172899B (en) * | 2012-12-24 | 2015-04-08 | 重庆大学 | Molecular imprinting composite membrane for organophosphorus pesticide detection and application of membrane |
| CN102977403A (en) * | 2012-12-24 | 2013-03-20 | 重庆大学 | Molecularly imprinted membrane based on porphyrin and acrylic monomers for organophosphorus pesticide and application thereof |
| CN103980524A (en) * | 2014-06-03 | 2014-08-13 | 吉首大学 | Preparation method and application of metal ion medium diosgenin imprinted polymer |
| CN103980524B (en) * | 2014-06-03 | 2016-03-23 | 吉首大学 | The preparation method of metal ion intermediary diosgenin imprinted polymer and application |
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| CN108892773A (en) * | 2018-05-07 | 2018-11-27 | 河南大学 | A kind of porphyrin polymer nano material, preparation method and application |
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| CN112409538B (en) * | 2019-11-29 | 2022-08-26 | 利宝莱科学有限公司 | Molecularly imprinted polymer capable of being combined with acetate, preparation method thereof, pharmaceutical composition containing molecularly imprinted polymer and pharmaceutical application of molecularly imprinted polymer |
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