CN103965401A - Preparation method and application of metal ion neutral-meson morpholine molecularly imprinted polymer - Google Patents
Preparation method and application of metal ion neutral-meson morpholine molecularly imprinted polymer Download PDFInfo
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- CN103965401A CN103965401A CN201410213643.4A CN201410213643A CN103965401A CN 103965401 A CN103965401 A CN 103965401A CN 201410213643 A CN201410213643 A CN 201410213643A CN 103965401 A CN103965401 A CN 103965401A
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- imprinted polymer
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Abstract
The invention discloses a preparation method and an application for a metal ion neutral-meson morpholine molecularly imprinted polymer. The method comprises the following steps of: (1) adding morpholine, 4-vinyl pyridine, metal cobalt (II) ions, dimethyl sulfoxide and acetonitrile in a container, ultrasonically preparing prepolymerization solution, standing, then adding EDMA (ethylene glycol dimethacrylate) and AIBN (2,2-azobisisobutyronitrile), charging argon, uniformly mixing, sealing, and reacting for 24 hours in a 60 DEG C water bath; and (2) after polymerization is finished, grinding, sieving, settling by using methyl alcohol and acetone, then eluting template molecule morpholine by using a solvent, and drying in vacuum. The morpholine molecularly imprinted polymer obtained by the method disclosed by the invention has high selective absorption capacity to the morpholine molecules, can be used for solid-phase extraction of morpholine, and is applicable to the needs of some special occasions.
Description
Technical field
The present invention relates to the Preparation method and use of a metal ion species intermediary morpholine molecularly imprinted polymer.
Background technology
Molecular imprinting is by artificial means preparation, target compound to be had the new technology of the molecularly imprinted polymer of height selective recognition performance.In general, be first that template molecule and function monomer pass through covalently or non-covalently effect formation function monomer-template molecule mixture, claim again host-guest coordination compound (Host-guest complex); Then add linking agent, by initiator initiated polymerization, generate highly cross-linked superpolymer, with solvent elution, remove the template molecule in superpolymer, thereby in molecularly imprinted polymer matrix, stay with template molecule in the trace hole matching aspect size, shape and function base, be imprinted sites, these adsorption sites have specific selectivity to target molecule.Molecularly imprinted polymer had both possessed the high selective recognition performance similar to biological antibody, again can be high temperature resistant, the severe rugged environment condition such as strong acid-base, there is good stability and higher work-ing life.Therefore molecularly imprinted polymer all shows good application prospect in fields such as chromatographic separation, solid phase extraction, enzyme simulation catalysis, clinical medicine analysis and sensor technologies.
It is separated that Solid-Phase Extraction utilizes solid adsorbent to realize each component adsorptive power difference in liquid sample.Because the selective recognition ability of molecularly imprinted polymer (MIP) is higher, for the selectivity of template material, far away higher than the conventional filler of Solid-Phase Extraction, stability is better, so MIP can be used as exclusive solid phase filler trace components is carried out to enrichment.Technology using MIP as solid phase extraction filler is called molecular engram solid phase extraction (molecular imprint solid phase extraction, MISPE) technology.
Morpholine claims again morpholine, and its chemical name is Isosorbide-5-Nitrae-morpholine, is a kind of colourless oil liquid under normal temperature.Be mainly used in the production of thiofide, also synthetic for tensio-active agent, textile auxiliary, medicine, agricultural chemicals.Morpholine is also as along catalyzer, corrosion inhibitor, optical bleaching agent polymerizing butadiene for, and morpholine is also the solvent of dyestuff, resin, wax, morning glue, casein food grade etc.Due to unique chemical property that morpholine has, become one of current Speciality Petrochemicals product with important commercial use, in industries such as rubber, medicine, agricultural chemicals, dyestuff, coating, there is purposes widely.In using the relative production process of morpholine, usually produce the trade effluent waste residue that some contain morpholine, if these refuses are directly discharged, not only can cause severe contamination to environment, and waste resource.Mainly by ion exchange method, reclaim morpholine at present, the trade effluent that contains morpholine, by cationic exchange resin adsorption, is then used to elutriant wash-out, remove after eluting solvent morpholine recoverable.This method operation steps is many, and the cycle is longer, and required equipment is many, and production capacity is restricted, and input cost is high.Molecular engram solid phase extraction is the high selective recognition performance to target molecule based on sorbing material, has improved extraction selectivity.
Summary of the invention
For promoting scientific-technical progress, develop the productivity, for the separation and purification of morpholine kind compound provides how selectable sorbent material, also make isolated morpholine kind compound purity higher, the inventor is through a large amount of scientific practices, finally invent a kind of morpholine molecularly imprinted polymer and preparation method thereof, utilize morpholine molecularly imprinted polymer prepared by the method to there is high selective recognition performance to morpholine kind compound, can be used as exclusive solid phase filler morpholine trace components is carried out to enrichment, possess stronger practical value.
For obtaining metal ion intermediary morpholine molecularly imprinted polymer, the present invention takes following processing step:
(1) in container, add morpholine, 0.4-0.8mmol4-vinyl pyridine, the cobalt metal ion of 0.3-0.6mol, 200ul dimethyl sulfoxide (DMSO), the 200ul acetonitrile of 0.1mmol, ultrasonic 10-20 minute makes pre-polymer solution, then standing 20-40min, add again 1-2mmolEDMA, 9mgAIBN, logical argon gas 10-20min, mix, sealing, reacts 24 hours in 60 ℃ of water-baths;
(2) after polymerization completes, grind, sieve, with methyl alcohol and acetone sedimentation, then the methyl alcohol-acetic acid mixed solvent wash-out template molecule morpholine that is 9:1 by volume ratio, until elutriant can't detect masterplate molecule, vacuum-drying 15-30h and get final product.
The present invention be take morpholine as template molecule, and cobalt metal ion (II) is intermediary, and 4-vinylpridine is function monomer, and ethylene glycol dimethacrylate acid is linking agent, and Diisopropyl azodicarboxylate is initiator, has prepared metal ion intermediary morpholine molecularly imprinted polymer.
The morpholine molecularly imprinted polymer that the present invention obtains has the selectivity of height and possesses certain adsorptive capacity morpholine molecule, thereby the morpholine molecularly imprinted polymer that the present invention can be obtained is for Solid-Phase Extraction, can make the separation of morpholine kind compound possess selectivity highly, adapt to the needs of some special occasions.
In order to investigate the adsorptive power of morpholine molecularly imprinted polymer to morpholine molecule, the inventor has drawn the adsorption isothermal line of morpholine molecularly imprinted polymer: take 1000mg morpholine and be dissolved in acetonitrile and be diluted to 100mL, be mixed with the morpholine acetonitrile mother liquor of 10 mg/mL.Get 10mg/mL mother liquor and be mixed with that concentration is 0.005,0.01,0.02,0.04,0.08,0.12,0.16,0.2,0.24,0.3,0.4,0.5, the morpholine acetonitrile solution 5mL of 1.0mg/mL, add respectively 5mg molecularly imprinted polymer, after Static Adsorption 6h, filter, filtrate constant volume is to 5mL, visible spectrophotometry test morpholine concentration wherein, and be calculated as follows equilibrium adsorption capacity Q
e(mg/g):
Q
e= ( C
o－ C
e) V/m
In formula, C
ofor starting point concentration (g/L), C
efor equilibrium concentration (g/L), V is liquor capacity (mL), and m is polymer quality (g).
Adsorption isothermal line has reflected the equilibrium adsorption capacity Q of polymkeric substance and the variation relation of equilibrium concentration C; increase along with morpholine concentration; equilibrium adsorption capacity increases gradually; finally tend towards stability; absorption reaches capacity; the maximal absorptive capacity of the morpholine molecular imprinting polymer that the present invention obtains can reach 212.8mg/g, and adsorptive power is very strong.
Compared with prior art, the invention has the beneficial effects as follows: invented a kind of new metal ion intermediary morpholine molecularly imprinted polymer and preparation method thereof, promoted effectively scientific-technical progress, for separation and purification morpholine kind compound provides how selectable sorbent material, also make isolated morpholine kind compound purity higher, utilize morpholine molecularly imprinted polymer prepared by the method morpholine kind compound to be there is to the selectivity of height, can be used as exclusive solid phase filler morpholine trace components is carried out to enrichment, possess stronger use value.
Embodiment
Below the Preparation method and use of metal ion intermediary morpholine molecularly imprinted polymer is elaborated.
embodiment 1:
(1) in container, add morpholine, 0.42mmol4-vinyl pyridine, the cobalt metal ion of 0.57mol, 200ul dimethyl sulfoxide (DMSO), the 200ul acetonitrile of 0.1mmol, within ultrasonic 12 minutes, make pre-polymer solution, then standing 37min, add again 1.1mmolEDMA, 9mgAIBN, logical argon gas 18min, mix, sealing, reacts 24 hours in 60 ℃ of water-baths;
(2) after polymerization completes, grind, sieve, with methyl alcohol and acetone sedimentation, then the methyl alcohol-acetic acid mixed solvent wash-out template molecule morpholine that is 9:1 by volume ratio, until elutriant can't detect masterplate molecule, vacuum-drying 16h and get final product.
The metal ion intermediary morpholine molecularly imprinted polymer that the present invention obtains has the selectivity of height and possesses certain adsorptive capacity morpholine molecule, thereby the morpholine molecularly imprinted polymer that the present invention can be obtained is for Solid-Phase Extraction, can make the separation of morpholine kind compound possess selectivity highly, adapt to the needs of some special occasions.
embodiment 2:
(1) in container, add morpholine, 0.77mmol4-vinyl pyridine, the cobalt metal ion of 0.31mol, 200ul dimethyl sulfoxide (DMSO), the 200ul acetonitrile of 0.1mmol, within ultrasonic 19 minutes, make pre-polymer solution, then standing 22min, add again 1.9mmolEDMA, 9mgAIBN, logical argon gas 11min, mix, sealing, reacts 24 hours in 60 ℃ of water-baths;
(2) after polymerization completes, grind, sieve, with methyl alcohol and acetone sedimentation, then the methyl alcohol-acetic acid mixed solvent wash-out template molecule morpholine that is 9:1 by volume ratio, until elutriant can't detect masterplate molecule, vacuum-drying 28h and get final product.
The metal ion intermediary morpholine molecularly imprinted polymer that the present invention obtains has the selectivity of height and possesses certain adsorptive capacity morpholine molecule, thereby the morpholine molecularly imprinted polymer that the present invention can be obtained is for Solid-Phase Extraction, can make the separation of morpholine kind compound possess selectivity highly, adapt to the needs of some special occasions.
Above-described embodiment is not done any pro forma restriction to the present invention, any those of ordinary skill in the art, in the situation that not departing from technical solution of the present invention scope, all can utilize the technology contents of above-mentioned announcement to make many possible changes and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not depart from technical solution of the present invention,, all should drop in the scope of technical solution of the present invention protection any simple modification made for any of the above embodiments, equivalent variations and modification according to the technology of the present invention essence.
Claims (4)
- The preparation method of 1.Yi metal ion species intermediary morpholine molecularly imprinted polymer, is characterized in that comprising following step:(1) in container, add morpholine, 0.4-0.8mmol4-vinyl pyridine, the cobalt metal ion of 0.3-0.6mol, 200ul dimethyl sulfoxide (DMSO), the 200ul acetonitrile of 0.1mmol, ultrasonic 10-20 minute makes pre-polymer solution, then standing 20-40min, add again 1-2mmolEDMA, 9mgAIBN, logical argon gas 10-20min, mix, sealing, reacts 24 hours in 60 ℃ of water-baths;(2) after polymerization completes, grind, sieve, with methyl alcohol and acetone sedimentation, then the methyl alcohol-acetic acid mixed solvent wash-out template molecule morpholine that is 9:1 by volume ratio, until elutriant can't detect masterplate molecule, vacuum-drying 15-30h and get final product.
- 2. the metal ion intermediary morpholine molecularly imprinted polymer that method obtains according to claim 1.
- 3. the metal ion intermediary morpholine molecularly imprinted polymer that method obtains is according to claim 1 as the method for solid extracting agent.
- 4. a solid extracting agent, is characterized in that: in solid extracting agent, include the metal ion intermediary morpholine molecularly imprinted polymer that method obtains described in claim 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254692A (en) * | 2015-11-27 | 2016-01-20 | 吉首大学 | Method for extracting aucubin and geniposide from eucommia ulmoides peel at same time |
| CN105466875A (en) * | 2015-11-23 | 2016-04-06 | 中国科学院青海盐湖研究所 | Method for measuring dodecylmorpholine |
| CN105820292A (en) * | 2016-04-19 | 2016-08-03 | 吉首大学 | Preparation method and application of molecularly imprinted polymer column capable of selectively removing methylbenzene and benzene |
| CN105854844A (en) * | 2016-06-07 | 2016-08-17 | 吉首大学 | Artemisinic acid magnetic imprinting microspheres and preparation method and application thereof |
| CN107722153A (en) * | 2017-11-13 | 2018-02-23 | 李辉 | A kind of Preparation method and use of more metal-complexing morphine trace high polymer new materials |
| CN111777713A (en) * | 2020-07-23 | 2020-10-16 | 福州大学 | Metal ion coordination bifunctional monomer molecularly imprinted polymer, and preparation method and application thereof |
| CN112159490A (en) * | 2020-10-16 | 2021-01-01 | 中国医学科学院药用植物研究所 | Polymer containing 2-morpholinyl ethyl methacrylate monomer unit and application |
-
2014
- 2014-05-21 CN CN201410213643.4A patent/CN103965401A/en active Pending
Non-Patent Citations (2)
| Title |
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| 李昱琢: "生物碱印迹聚合物的制备及其吸附行为研究", 《吉首大学硕士学位论文》 * |
| 王岩等: "烯酰吗啉分子印迹聚合物的合成及固相萃取研究", 《广东化工》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105466875A (en) * | 2015-11-23 | 2016-04-06 | 中国科学院青海盐湖研究所 | Method for measuring dodecylmorpholine |
| CN105254692A (en) * | 2015-11-27 | 2016-01-20 | 吉首大学 | Method for extracting aucubin and geniposide from eucommia ulmoides peel at same time |
| CN105254692B (en) * | 2015-11-27 | 2017-10-24 | 吉首大学 | It is a kind of at the same extract Bark of Eucommia Ulmoides in aucubin and geniposide method |
| CN105820292A (en) * | 2016-04-19 | 2016-08-03 | 吉首大学 | Preparation method and application of molecularly imprinted polymer column capable of selectively removing methylbenzene and benzene |
| CN105854844A (en) * | 2016-06-07 | 2016-08-17 | 吉首大学 | Artemisinic acid magnetic imprinting microspheres and preparation method and application thereof |
| CN105854844B (en) * | 2016-06-07 | 2018-01-26 | 吉首大学 | Arteannuic acid magnetic blotting microballoon and its preparation method and application |
| CN107722153A (en) * | 2017-11-13 | 2018-02-23 | 李辉 | A kind of Preparation method and use of more metal-complexing morphine trace high polymer new materials |
| CN107722153B (en) * | 2017-11-13 | 2019-11-29 | 骆雅雅 | A kind of Preparation method and use of more metal coordination morphine trace high polymer new materials |
| CN111777713A (en) * | 2020-07-23 | 2020-10-16 | 福州大学 | Metal ion coordination bifunctional monomer molecularly imprinted polymer, and preparation method and application thereof |
| CN112159490A (en) * | 2020-10-16 | 2021-01-01 | 中国医学科学院药用植物研究所 | Polymer containing 2-morpholinyl ethyl methacrylate monomer unit and application |
| CN112159490B (en) * | 2020-10-16 | 2022-03-11 | 中国医学科学院药用植物研究所 | Polymer containing 2-morpholinyl ethyl methacrylate monomer unit and application |
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Application publication date: 20140806 |