CN101648132A - Method for preparing hydrophilic molecular imprinting microsphere by using ionic liquid as novel functional monomer by suspension method - Google Patents
Method for preparing hydrophilic molecular imprinting microsphere by using ionic liquid as novel functional monomer by suspension method Download PDFInfo
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- CN101648132A CN101648132A CN200910115863A CN200910115863A CN101648132A CN 101648132 A CN101648132 A CN 101648132A CN 200910115863 A CN200910115863 A CN 200910115863A CN 200910115863 A CN200910115863 A CN 200910115863A CN 101648132 A CN101648132 A CN 101648132A
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Abstract
The invention relates to a method for preparing hydrophilic molecular imprinting microsphere by using ionic liquid as a novel functional monomer by a suspension method. The method is characterized bycomprising the following steps: (1) synthesizing iminazole type ionic liquid with double-bond carboxylic acid by using alkyl imidazole and brominated trialkyl crylic acid; (2) adding a dispersing agent into water and stirring the water until the dispersing agent is fully dissolved; (3) carrying out self-assembly on template molecules and functional monomers; (4) mixing trimethylolpropane trimethacrylate, an initiating agent and a diluent; (5) mixing the three solutions, leading N2 to an obtained mixed solution and then sealing the mixed solution; (6) washing a polymer obtained by the reactionby an organic solvent; and (7) airing the polymer at normal temperature to obtain the hydrophilic molecular imprinting microsphere. The invention has the advantages that the synthesized molecular imprinting polymer has the characteristics of controllable size, strong rigidity, good hydrophilicity and high selectivity and is quite suitable for the enrichment, the separation and the analysis of analogs in foods, biological samples and aquatic environment samples.
Description
Technical field
The present invention relates to a kind ofly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method with ionic liquid.
Background technology
In recent years along with molecular imprinting research deeply and the expansion of application, the technology of preparing of molecularly imprinted polymer (MIP) and performance study are subjected to various countries scholar's extensive concern and great attention.But the technology of preparing of MIP is mainly based on polymerisation in bulk, and the product that makes can use behind grinding, the particle that obtains required size that sieves for block.Yet grinding can cause the part conjugated group to be destroyed, thereby molecular recognition is descended with selecting performance, and the gained shape of particle is irregular, the dispersiveness is relatively poor.In addition, product loss is serious in the process of lapping, and the adsorption site utilization rate is not high.By contrast, directly not only shape is regular, specific area is big, high adsorption capacity, particle diameter are controlled for He Cheng MIP microballoon, and postprocessing working procedures is simple, only need just can directly use the template molecule wash-out, so the preparation of MIP microballoon and application study are just becoming the focus that molecular imprinting is studied.
On the other hand, the preparation of present most molecularly imprinted polymers and application all are confined to carry out in the organic solvent, and natural recognition system and the actual application environment that MIP faced are then mostly to be water-based systems.Because hydrone damages the combination between microsphere and the functional group especially hydrogen bond easily, if the condition of trace is selected the improper failure that just causes trace probably.Yet the trace in the organic solvent is not simulated the water environment in the practical application as a rule again, can not satisfy the diversified demand of actual environment for use.In water environment, carry out molecular recognition, require polymer to have enough hydrophilies.It is monomer that acrylic acid derivative (as methacrylic acid MAA) and vinylpyridine (4-VP) are adopted in organic synthesis usually, and GDMA (EDMA) is a crosslinking agent; And in water is synthetic, pre-organized the mistake between range request microsphere and the monomer before the polymerization will have sufficient touch opportunity and environment, so that each relevant group can be arranged and compound mode for specific identification effect in the future obtains necessary space, require microsphere in the pre-polymerization dicyandiamide solution, to have certain solubility for this reason.Thereby, seek or monomer synthetic and that water soluble molecules has the effect of well dissolving each other, be a basic premise of the desirable MIP material of preparation.
At present, have some water miscible monomers to be used to the synthetic of MIP, comprise methacryl antipyrine (MAAP) [
A, Denizli A, Sener I, et al.Sep.Purif.Technol., 2004,38:173-179], 2-hydroxymethyl ethyl acrylate, N, N, N-Trimethylamine ethyl-methyl acrylate and ferric protoporphyrin [Cheng ZY, Zhang LW, Li YZ.Chem.Eur.J., 2004,10:3555-3561] etc.Defectives such as type of action not strong, the group of being correlated with only is confined to hydrogen bond action but also there is hydrophily in existing hydrophilic monomer, and trace efficient is low.With strongly hydrophilic and there is the monomer of multiple type of action, the preparation method of synthesizing efficient molecularly imprinted polymer awaits further developing.
Summary of the invention
The object of the present invention is to provide and a kind ofly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method with ionic liquid, it is as function monomer with imidazole type ion liquid with two key carboxylic acids, utilize the hydrogen bond of template molecule and ionic liquid function monomer, multidigit point such as hydrophobic effect and electrostatic interaction synergy realizes the high selectivity of MIP microballoon aqueous phase, prepare hydrophilic molecular imprinting microsphere with ionic liquid as the novel functional monomer suspension method, it is regular to have shape, controllable size, advantages such as specific area is big have been expanded the preparation method and the scope of application of hydrophilic molecular imprinting polymer.
The present invention is achieved like this, and it is characterized in that method step is:
(1) with alkyl imidazole and the synthetic imidazole type ion liquid of bromo alkyl acrylic with two key carboxylic acids;
(2) dispersant is placed water, be stirred to its whole dissolvings, and be heated to 65-95 ℃;
(3) with the self assembly in hydrophilic solvent of template molecule, function monomer, the mol ratio of template molecule, function monomer, hydrophilic solvent is 1: 2～6: 2～6;
(4), stir with trimethylol-propane trimethacrylate, initator and mixing diluents;
(5) above-mentioned three kinds of solution are mixed, feed N
2Airtight behind the 5-10min, stirred 6-10 hour in the constant speed of 65-80 ℃ of constant temperature with 300-400rpm;
(6) polymer that reaction is obtained cleans with organic solvent earlier, uses the dilute acid soln wash-out again, to removing template molecule;
(7) polymer that will remove template molecule washes with water to neutrality, dries at normal temperatures, promptly gets the hydrophilic molecular imprinting polymer.
The imidazole type ion liquid of of the present invention pair of key carboxylic acid be in bromination 1-(α-Jia Jibingxisuan)-3-methylimidazole, bromination 1-(α-Jia Jibingxisuan)-3-ethyl imidazol(e), bromination 1-(butenoic acid)-3-methylimidazole, bromination 1-(the butenoic acid)-3-ethyl imidazol(e) any one.
Dispersant of the present invention is polyvinyl alcohol or methylcellulose.
Diluent of the present invention is any one in toluene, carbon tetrachloride, the acetonitrile, and described initator is an azodiisobutyronitrile.
Hydrophilic solvent of the present invention is a water.
The synthetic route of function monomer of the present invention is:
The hydrophilic molecular imprinting microsphere preparation process is as follows among the present invention:
Advantage of the present invention is: the synthetic molecularly imprinted polymer of this method has that controllable size, rigidity are strong, good hydrophilic property, characteristics that selectivity is high, be very suitable for the analogue in food, biological sample and the water environment sample enrichment, separate and analysis.
Description of drawings
Fig. 1 is isothermal curve figure of the present invention.
The specific embodiment
Reagent of the present invention and material
Polyvinyl alcohol (PVA124), chemical pure.
It is pure that caffeine, theophylline, fly eradication amine, trimethylol-propane trimethacrylate TRIM, azodiisobutyronitrile, methyl alcohol, acetonitrile, carbon tetrachloride, toluene and other solvents are analysis.
Bromination 1-(α-Jia Jibingxisuan)-3-methylimidazole, bromination 1-(α-Jia Jibingxisuan)-3-ethyl imidazol(e), bromination 1-(butenoic acid)-3-methylimidazole, bromination 1-(butenoic acid)-3-ethyl imidazol(e) are that oneself is synthetic, by IR, HNMR characterize, high-efficient liquid phase chromatogram determining content is more than 95%.
Embodiment 1
With the PVA124 of 6.0000g, the four-hole bottle that 150mL water places 250mL, stirring makes it dissolving and is heated to 85-90 ℃.0.6880g α-Jia Jibingxisuan function monomer and theophylline are dissolved in the 20mL water, also add in the four-hole bottle.The toluene of 13.5200g TRIM, 0.2000g AIBN and 10mL mixes, stirs then, adds in the four-hole bottle after the AIBN dissolving, feeds N
2Airtight behind the 5min, constant temperature (75 ℃), constant speed (365rpm) stir the 8h reaction and finish.
Elution process
The polymer of reaction gained is cleaned twice with 100mL acetone and ethanol earlier; Use V again
(methyl alcohol): V
(acetate)=9: 1 eluant solution, caffeine can not detect microsphere in high performance liquid chromatography in eluent, cleans repeatedly to neutrality with deionized water again, the polymer behind the wash-out is dried at normal temperatures promptly to get MIPs at last.When with coffee because competition during substrate, the separation factor of resulting polymers in water environment is 1.12, when with fly eradication amine serving as the competition substrate, separation factor is 1.31.The microballoon average out to 50 μ m of resulting polymers.
Embodiment 2
With the PVA124 of 6.0000g, the four-hole bottle that 150mL water places 250mL, stirring makes it dissolving and is heated to 85-90 ℃.Synthetic 2.0000 ionic liquid function monomers and 0.3883g caffeine are dissolved in the 20mL water, also add in the four-hole bottle.The toluene of 13.5200g TRIM, 0.2000g AIBN and 10mL mixes, stirs then, adds in the four-hole bottle after the AIBN dissolving, feeds N
2Airtight behind the 5min, constant temperature (75 ℃), constant speed (365rpm) stir the 8h reaction and finish.As shown in Figure 1, abscissa is represented the initial solubility of caffeine, and ordinate is represented temperature, along with the increase temperature of caffeine solubility also in continuous rising.
Elution process is the same
When with the theophylline being the competition substrate, the separation factor of resulting polymers in water environment is 1.91, and when with fly eradication amine serving as the competition substrate, separation factor is 3.57.The microballoon average out to 50 μ m of resulting polymers.
Embodiment 3
With the PVA124 of 6.0000g, the four-hole bottle that 150mL water places 250mL, stirring makes it dissolving and is heated to 85-90 ℃.Novel functional monomer and 0.3603g theophylline that 2.0000g is synthetic are dissolved in the 20mL water, also add in the four-hole bottle.The toluene of 13.5200g TRIM, 0.2000g AIBN and 10mL mixes, stirs then, adds in the four-hole bottle after the AIBN dissolving, feeds N
2Airtight behind the 5min, constant temperature (75 ℃), constant speed (365rpm) stir the 8h reaction and finish.
Elution process is the same
When with coffee because competition during substrate, the separation factor of resulting polymers in water environment is 1.41, when with fly eradication amine serving as the competition substrate, separation factor is 6.51.The microballoon average out to 50 μ m of resulting polymers.
Embodiment 4
With the MC (methylcellulose) of 1.0000g, the four-hole bottle that 150mL water places 250mL, stirring makes it dissolving and is heated to 85-90 ℃.Novel functional monomer and 0.3884g caffeine that 2.0000g is synthetic are dissolved in the 20mL water, also add in the four-hole bottle.The toluene of 13.5200g TRIM, 0.2000g AIBN and 10mL mixes, stirs then, adds in the four-hole bottle after the AIBN dissolving, feeds N
2Airtight behind the 5min, constant temperature (75 ℃), constant speed (365rpm) stir the 8h reaction and finish.
Elution process is the same
When with the theophylline being the competition substrate, the separation factor of resulting polymers in water environment is 2.35, and when with fly eradication amine serving as the competition substrate, separation factor is 7.22.The microballoon average out to 50 μ m of resulting polymers.
Claims (5)
1, a kind ofly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method, it is characterized in that method step is with ionic liquid:
(1) with alkyl imidazole and the synthetic imidazole type ion liquid of bromo alkyl acrylic with two key carboxylic acids;
(2) dispersant is placed water, be stirred to its whole dissolvings, and be heated to 65-95 ℃;
(3) with the self assembly in hydrophilic solvent of template molecule, function monomer, the mol ratio of template molecule, function monomer, hydrophilic solvent is 1: 2～6: 2～6;
(4), stir with trimethylol-propane trimethacrylate, initator and mixing diluents;
(5) above-mentioned three kinds of solution are mixed, feed N
2Airtight behind the 5-10min, stirred 6-10 hour in the constant speed of 65-80 ℃ of constant temperature with 300-400rpm;
(6) polymer that reaction is obtained cleans with organic solvent earlier, uses the dilute acid soln wash-out again, to removing template molecule;
(7) polymer that will remove template molecule washes with water to neutrality, dries at normal temperatures, promptly gets the hydrophilic molecular imprinting polymer.
2, according to claim 1ly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method with ionic liquid, the imidazole type ion liquid that it is characterized in that described pair of key carboxylic acid be in bromination 1-(α-Jia Jibingxisuan)-3-methylimidazole, bromination 1-(α-Jia Jibingxisuan)-3-ethyl imidazol(e), bromination 1-(butenoic acid)-3-methylimidazole, bromination 1-(the butenoic acid)-3-ethyl imidazol(e) any one.
3, according to claim 1ly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method, it is characterized in that described dispersant is polyvinyl alcohol or methylcellulose with ionic liquid.
4, according to claim 1ly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method with ionic liquid, it is characterized in that described diluent is any one in toluene, carbon tetrachloride, the acetonitrile, described initator is an azodiisobutyronitrile.
5, according to claim 1ly prepare hydrophilic molecular imprinting microsphere as the novel functional monomer suspension method, it is characterized in that described hydrophilic solvent is a water with ionic liquid.
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| CN102974285A (en) * | 2012-12-03 | 2013-03-20 | 南京大学 | Producing method of magnetic microsphere with hierarchical-pore structure and adjustable uniform grain size |
| CN103113520A (en) * | 2013-01-23 | 2013-05-22 | 南昌航空大学 | Method for preparing ionic imprinting microsphere by taking crown ether as functional monomer in inverse emulsion method |
| CN103191706A (en) * | 2013-04-07 | 2013-07-10 | 江苏大学 | Preparation method of 2,5- dyhydroxyl benzoic acid molecule blotting membrane and application of 2,5- dyhydroxyl benzoic acid molecule blotting membrane |
| CN104289207A (en) * | 2014-09-28 | 2015-01-21 | 天津医科大学 | Method for preparing monolithic liquid crystal molecular imprinting column by using chiral molecules as doping agent |
| CN104892839A (en) * | 2015-06-23 | 2015-09-09 | 嘉兴学院 | Surface molecular imprinting polyion liquid of reduced graphene oxide for detecting bisphenol A and preparation method and application of surface molecular imprinting polyion liquid |
| CN108393075A (en) * | 2018-03-08 | 2018-08-14 | 陕西科技大学 | A kind of ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application |
| CN110183816A (en) * | 2019-06-03 | 2019-08-30 | 辽宁大学 | A kind of polymer composite microballoon and preparation method thereof |
| US20210032394A1 (en) * | 2019-07-30 | 2021-02-04 | Seiko Epson Corporation | Polymer Dispersant, Colorant Dispersion Liquid, And Ink Composition |
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- 2009-09-02 CN CN2009101158632A patent/CN101648132B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974285A (en) * | 2012-12-03 | 2013-03-20 | 南京大学 | Producing method of magnetic microsphere with hierarchical-pore structure and adjustable uniform grain size |
| CN103113520A (en) * | 2013-01-23 | 2013-05-22 | 南昌航空大学 | Method for preparing ionic imprinting microsphere by taking crown ether as functional monomer in inverse emulsion method |
| CN103113520B (en) * | 2013-01-23 | 2014-12-10 | 南昌航空大学 | Method for preparing ionic imprinting microsphere by taking crown ether as functional monomer in inverse emulsion method |
| CN103191706A (en) * | 2013-04-07 | 2013-07-10 | 江苏大学 | Preparation method of 2,5- dyhydroxyl benzoic acid molecule blotting membrane and application of 2,5- dyhydroxyl benzoic acid molecule blotting membrane |
| CN103191706B (en) * | 2013-04-07 | 2015-02-04 | 江苏大学 | Preparation method of 2,5- dyhydroxyl benzoic acid molecule blotting membrane and application of 2,5- dyhydroxyl benzoic acid molecule blotting membrane |
| CN104289207A (en) * | 2014-09-28 | 2015-01-21 | 天津医科大学 | Method for preparing monolithic liquid crystal molecular imprinting column by using chiral molecules as doping agent |
| CN104892839A (en) * | 2015-06-23 | 2015-09-09 | 嘉兴学院 | Surface molecular imprinting polyion liquid of reduced graphene oxide for detecting bisphenol A and preparation method and application of surface molecular imprinting polyion liquid |
| CN108393075A (en) * | 2018-03-08 | 2018-08-14 | 陕西科技大学 | A kind of ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application |
| CN108393075B (en) * | 2018-03-08 | 2021-05-04 | 陕西科技大学 | Ionic liquid modified cellulose-based adsorbent and preparation method and application thereof |
| CN110183816A (en) * | 2019-06-03 | 2019-08-30 | 辽宁大学 | A kind of polymer composite microballoon and preparation method thereof |
| US20210032394A1 (en) * | 2019-07-30 | 2021-02-04 | Seiko Epson Corporation | Polymer Dispersant, Colorant Dispersion Liquid, And Ink Composition |
| US11851517B2 (en) * | 2019-07-30 | 2023-12-26 | Seiko Epson Corporation | Polymer dispersant, colorant dispersion liquid, and ink composition |
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