CN101423612A - Method for preparing silica gel surface phenols molecularly imprinted polymer - Google Patents
Method for preparing silica gel surface phenols molecularly imprinted polymer Download PDFInfo
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- CN101423612A CN101423612A CNA200810080050XA CN200810080050A CN101423612A CN 101423612 A CN101423612 A CN 101423612A CN A200810080050X A CNA200810080050X A CN A200810080050XA CN 200810080050 A CN200810080050 A CN 200810080050A CN 101423612 A CN101423612 A CN 101423612A
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Abstract
The invention relates to a method for synthesizing surface molecular engram materials, in particular to a method for preparing phenol molecular engram polymers on the surface of silica gel, which solves the problems in the prior surface molecular engram polymers of low molecular weight of functional macromolecules, low content of functional groups, low grafting percent of engram materials and so on. The method comprises the following steps: firstly, the silica gel is activated, reacts with a coupling agent, and reacts with a polymine aqueous solution; secondly, the surface of the silica gel is chemically grafted with polymine to prepare a grafting material PEI/SiO2; thirdly, the grafting material PEI/SiO2 which absorbs template molecules to be balanced is added into an ethanol aqueous solution of a crosslinking agent for reaction; and fourthly, reacted materials are repeatedly washed by a hydrochloric acid for removal of the template molecules, washed by distilled water to neutralization, and subjected to vacuum drying. The preparation process is simple, and the silica gel surface engram materials prepared have high absorption capacity and superior absorption selectivity on the template molecules, have actuating locus inside silica gel surface polymer films, have small diffusion resistance and quick mass transfer speed, and are easy to achieve absorption equilibrium.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular engram material, be specially a kind of preparation method of silica gel surface phenols molecularly imprinted polymer.
Background technology
Aldehydes matter is a kind of persistence organic pollutant, extensively is present in the sewage of medicine, dyestuff, photograph and agrochemicals industry, human and other organism is had extremely harm such as teratogenesis, carcinogenic, mutagenesis.Owing to have high toxicity and can in environment, accumulate and be difficult for being decomposed, contain the phenol pollutent and caused a series of environmental problem, in primary pollutant is listed it by Environmental Protection Agency.
Now both at home and abroad the treatment process to phenolic wastewater mainly contains following several method, adsorbs with inorganic porous material such as gac, wilkinite and synthetic polymer materials, carries out degradation treatment with biological bacterium or some catalyzer.Traditional sorbing material adsorption efficiency is low, the salvage material difficulty, and repeat usage is low, and does not have selectivity.Conditional request harshness in needed microbial culture process and treating processes during degradation treatment waste water, and process cost height are difficult for promoting big area and use, and the degraded of general catalyst exist shortcomings such as efficient is low equally.
(Molecular Imprint Polymer MIP) is a kind of polymer materials with molecule distinguishability to molecularly imprinted polymer.The traditional method of preparation molecularly imprinted polymer is an entrapping method, promptly in the presence of template molecule, function monomer and linking agent generation copolymerization (or crosslinkable function macromole generation crosslinked action), owing to there is covalently or non-covalently (hydrogen bond between template molecule and the function monomer (or function macromole), the metal-complexing key, electrostatic attraction etc.) effect, function monomer just can be arranged in around the template molecule in a certain order, remove template molecule after the polymerization, in polymkeric substance, just stay and template molecule space structure and action site complementary hole, thereby make imprinted polymer produce strong memory and recognition function, show special affinity of template molecule and good adsorption selectivity energy to template molecule.Molecularly imprinted polymer is to the recognition performance of template molecule brilliance, make it bring into play vital role, such as being used for Solid-Phase Extraction, chromatographic separation, membrane sepn, biosensor, drug release, simulation transition state catalyzer and mimetic enzyme catalysis etc. at numerous sciemtifec and technical spheres.But the molecularly imprinted polymer of traditional method preparation to template molecule embedding cross dark or tension, wash-out difficulty not only, and because the duct is dark, and the template molecule diffusional resistance is big, and mass transfer velocity is slow, be difficult for combining with recognition site makes the reduction of useful space amount.
For overcoming above-mentioned shortcoming effectively, some investigators had explored a kind of surface imprinted technology in recent years, were about to silica-gel carrier, polymerization single polymerization monomer, linking agent, template molecule mixing, after the reaction template molecule flush away had promptly been made surface imprinted material.At first the silica gel surface physics is applied one deck chitosan such as people such as Su Haijia, add the linking agent epoxy chloropropane behind the adsorbing metal ions and carry out crosslinkedly, slough the hole that has stayed metal ion behind the metal ion on the silica gel surface at last; People such as Li Feng have also done akin research, the imprinted material that this method makes is because function macromole molecular weight is low, and functional group content is few, so adsorptive capacity is very little, and functional polymer and silica gel just rely on physical adsorption to interact the mechanics of materials less stable of preparation.People such as Zhu Lihua mix activated silica gel, function monomer and phenols, form composite precursor, oxypolymerization is crosslinked then, removes behind the target molecule and forms one deck imprinted polymer on the silica gel surface, and this method is when crosslinking reaction, the function monomer that is dissolved in a large number in the solvent can at first carry out polyreaction, form traditional imprinted polymer, cause the function monomer utilization ratio low, and the imprinted material percentage of grafting that makes is low, loading capacity is little, and adsorption efficiency is low.
Summary of the invention
There are problems such as the imprinted material percentage of grafting that function macromole molecular weight is low, functional group content is few, utilization ratio is low and obtain is low, loading capacity is little, mechanical stability is relatively poor in the present invention in order to solve existing silica gel surface imprinted polymer, and a kind of preparation method of silica gel surface phenols molecularly imprinted polymer is provided.
The present invention adopts following technical scheme to realize: a kind of preparation method of silica gel surface phenols molecularly imprinted polymer may further comprise the steps: the activation of (1) silica gel; (2) silica gel surface chemistry key connects alkylogen: the silica gel after 5～10g activation is joined in the four-hole boiling flask of 100mL, adding 40～60mL organic solvent and 1～5mL water again is stirring solvent, add the halogen-containing silane coupling agent of 10～15mL then, react 6～8h down at 70～80 ℃, after reaction finishes product is used toluene extracting 24～30h in Soxhlet extractor, remove unreacted silane coupling agent in the system, at last vacuum-drying 24～30h in vacuum drying oven; (3) silica gel surface chemistry grafting polyethylene imine PEI: measuring 50～60mL mass ratio with graduated cylinder is the four-hole boiling flask that 30～50% polyethyleneimine: amine aqueous solution places 100mL, take by weighing the silica gel that obtains in 1～4g above-mentioned steps (2) again and place four-hole boiling flask, 90 ℃ of back flow reaction 5～7h, reaction finishes back distilled water flushing product, suction filtration promptly makes sorbing material PEI/SiO after 34～40 ℃ of vacuum-dryings in vacuum drying oven
2(4) preparation of silica gel molecular imprinted polymer on surface: 1～4g is adsorbed the template molecule aldehydes matter to equilibrated graft materials PEI/SiO
2Mix with the aqueous ethanolic solution of 5～8mL linking agent, with the pH of sodium hydroxide solution regulation system between 8 to 11, at 20～50 ℃ of following stirring reaction 3～6h, after reaction finishes, suction filtration, use the hydrochloric acid repetitive scrubbing again, suction filtration is used the distilled water repetitive scrubbing then, suction filtration, till filtrate was neutrality, 35～40 ℃ of vacuum-dryings in vacuum drying oven then made silica gel surface phenols molecularly imprinted sorbing material MIP-PEI/SiO
2Described template molecule aldehydes matter can be all aldehydes matters of mentioning in the background technology, and different aldehydes matters all can prepare corresponding molecular imprinting sorbing material according to the method described above.
Can adopt existing a lot of methods for silica gel activating, the method that the present invention adopts is that 5～10g silica gel is joined 30～60mL concentration is in 5%～20% the aqueous hydrochloric acid, at 90 ℃ of following stir-activatings, make the silica gel surface have more hydroxyl, behind activation 4～8h, filter, with distilled water thorough washing filter cake, vacuum-drying 24～30h in vacuum drying oven promptly obtains activatory silica gel at last.
Described halogen-containing silane coupling agent is any one in γ-r-chloropropyl trimethoxyl silane or γ-bromopropyl Trimethoxy silane or the γ-iodine propyl trimethoxy silicane.
Described linking agent is ethylene glycol diglycidylether or 1,4-dichlorobutane or 1, any one in 6-dichloro hexane or the epoxy chloropropane.
In order to further specify preparation process of the present invention, with halogen-containing silane γ-r-chloropropyl trimethoxyl silane be coupling agent, when ethylene glycol diglycidylether is linking agent, reaction formula is expressed as follows:
The chemical graft silane coupling agent:
Chemical graft PEI:
The trace process:
The present invention at first with the functional polymer chemical graft on the silica gel surface, then phenolic compound is adsorbed, add linking agent again and carry out crosslinkedly, remove the imprinted polymer film that contains a large amount of functional groups that has formed one deck chemical graft behind the template molecule on the silica gel surface at last.The preparation process of present method is simple, prepared silica gel surface imprinted material has high loading capacity and good adsorption selectivity to template molecule, can realize to template molecule high-adsorption-capacity, height selectively adsorb, separation and enrichment, and action site is in the polymer foil on silica gel surface, diffusional resistance is little, mass transfer velocity is fast, reach adsorption equilibrium easily, be applicable to solid phase selective extraction and Modern Analytical Instrument coupling new technology, for the preparation of aldehydes matter molecularly imprinted polymer provides a kind of feasible preparation scheme.
Embodiment
Embodiment 1:
A kind of preparation method of silica gel surface phenols molecularly imprinted polymer, may further comprise the steps: the activation of (1) silica gel: it is in 5% the aqueous hydrochloric acid that 5g silica gel is joined 30mL concentration, at 90 ℃ of following stir-activatings, behind the activation 4h, filter, with distilled water thorough washing filter cake, vacuum-drying 24h in vacuum drying oven promptly obtains activatory silica gel at last; (2) silica gel surface chemistry key connects alkylogen: the silica gel after the 5g activation is joined in the four-hole boiling flask of 100mL, adding 40mL toluene and 1mL water again is stirring solvent, add 10mL γ-r-chloropropyl trimethoxyl silane then, react 6h down at 70 ℃, after reaction finishes product is used toluene extracting 24h in Soxhlet extractor, remove unreacted silane coupling agent in the system, vacuum-drying 24h in vacuum drying oven at last obtains the silica gel (CP-SiO of chloropropylation
2); (3) silica gel surface chemistry grafting polyethylene imine PEI: measuring the 50mL mass ratio with graduated cylinder is the four-hole boiling flask that 30% polyethyleneimine: amine aqueous solution places 100mL, take by weighing the silica gel that obtains in the 1g above-mentioned steps (2) again and place four-hole boiling flask, 90 ℃ of back flow reaction 5h, reaction finishes back distilled water flushing product, suction filtration promptly makes sorbing material PEI/SiO after 34 ℃ of vacuum-dryings in vacuum drying oven
2(4) preparation of silica gel molecular imprinted polymer on surface: accurately take by weighing 1g sorbing material PEI/SiO
2, be 1000mgL with 1000mL concentration then
-1 p-nitrophenyl phenol solution is mixed in tool plug Erlenmeyer flask, and constant temperature vibration 10h in the gas bath constant temperature oscillator makes absorption reach balance then, uses the distilled water repetitive scrubbing then, and suction filtration is dried in vacuum drying oven then.The sorbing material PEI/SiO that 1g has been adsorbed the template molecule aldehydes matter
2Mix with the aqueous ethanolic solution of 5mL ethylene glycol diglycidylether, pH with the sodium hydroxide solution regulation system is 8, at 20 ℃ of following stirring reaction 3h, after reaction finishes, suction filtration, use the hydrochloric acid repetitive scrubbing again, suction filtration is used the distilled water repetitive scrubbing then, suction filtration, till filtrate was neutrality, 35 ℃ of vacuum-dryings in vacuum drying oven then made silica gel surface p-NP molecular imprinting sorbing material MIP-PEI/SiO
2
Get and move 50mL1000mgL
-1P-NP, m-nitro phenol solution, place 100mL tool plug Erlenmeyer flask to mix, take by weighing p-NP molecular imprinting sorbing material MIP-PEI/SiO of about 0.1g again
2Put in the above-mentioned solution, constant temperature vibration 10h in the gas bath constant temperature oscillator then, after the adsorption equilibrium, solution centrifugal is separated, measure the concentration of p-NP and m-nitrophenol in the solution respectively, calculate the equilibrium adsorption capacity of two kinds of materials according to formula (1), calculate MIP-PEI/SiO according to formula (2) and formula (3)
2Partition ratio K to two kinds of materials
dAnd selectivity coefficient k, the results are shown in table 1:
In the formula, Q
e(mgg
-1) be equilibrium adsorption capacity; V (L) is the volume of solution; C
0(mgL
-1) be initial concentration of solution; C
e(mgL
-1) be equilibrium concentration; M (g) is MIP-PEI/SiO
2Quality.
In the formula, Q
e(mgg
-1) be equilibrium adsorption capacity; C
e(mgL
-1) be equilibrium concentration.
In the formula, K
d(A) be MIP-PEI/SiO
2Partition ratio to template molecule; K
d(B) be MIP-PEI/SiO
2Partition ratio to the reference molecule.
Get and move 50mL1000mgL
-1P-NP, para-chlorophenol solution, place 100mL tool plug Erlenmeyer flask to mix, take by weighing p-NP molecular imprinting sorbing material MIP-PEI/SiO of about 0.1g again
2Put in the solution, constant temperature vibration 10h in the gas bath constant temperature oscillator after the adsorption equilibrium, separates solution centrifugal then, measure the concentration of p-NP and para-chlorophenol in the solution respectively, calculate the equilibrium adsorption capacity and the MIP-PEI/SiO of two kinds of materials according to above-mentioned formula
2Partition ratio K to two kinds of materials
dAnd selectivity coefficient k, the results are shown in table 1.
Table 1:MIP-PEI/SiO
2Partition ratio and selectivity coefficient to different aldehydes matters
Can find out the silica gel surface p-NP molecular imprinting sorbing material MIP-PEI/SiO that makes according to embodiment 1 described method by above table
2Partition ratio to p-NP is far longer than m-nitrophenol, para-chlorophenol.
Embodiment 2:
A kind of preparation method of silica gel surface phenols molecularly imprinted polymer, may further comprise the steps: the activation of (1) silica gel: it is in 20% the aqueous hydrochloric acid that 10g silica gel is joined 60mL concentration, at 90 ℃ of following stir-activatings, behind the activation 8h, filter, with distilled water thorough washing filter cake, vacuum-drying 30h in vacuum drying oven promptly obtains activatory silica gel at last; (2) silica gel surface chemistry key connects alkylogen: the silica gel after the 10g activation is joined in the four-hole boiling flask of 100mL, adding 60mL dimethylbenzene and 5mL water again is stirring solvent, add 15mL γ-bromopropyl Trimethoxy silane then, react 8h down at 80 ℃, after reaction finishes product is used toluene extracting 30h in Soxhlet extractor, remove unreacted silane coupling agent in the system, vacuum-drying 30h in vacuum drying oven at last obtains the silica gel of bromopropylization; (3) silica gel surface chemistry grafting polyethylene imine PEI: measuring the 60mL mass ratio with graduated cylinder is the four-hole boiling flask that 50% polyethyleneimine: amine aqueous solution places 100mL, take by weighing the silica gel that obtains in the 4g above-mentioned steps (2) again and place four-hole boiling flask, 90 ℃ of back flow reaction 7h, reaction finishes back distilled water flushing product, suction filtration promptly makes sorbing material PEI/SiO after 40 ℃ of vacuum-dryings in vacuum drying oven
2(4) preparation of silica gel molecular imprinted polymer on surface: 4g is adsorbed the template molecule para-chlorophenol to equilibrated graft materials PEI/SiO
2With 8mL1, the aqueous ethanolic solution of 4-dichlorobutane mixes, and the pH that uses the sodium hydroxide solution regulation system is 11, at 50 ℃ of following stirring reaction 6h, after reaction finished, suction filtration was used the hydrochloric acid repetitive scrubbing again, suction filtration, use the distilled water repetitive scrubbing then, suction filtration is till filtrate is neutrality, 40 ℃ of vacuum-dryings in vacuum drying oven then make silica gel surface para-chlorophenol molecular imprinting sorbing material MIP-PEI/SiO
2
Embodiment 3:
A kind of preparation method of silica gel surface phenols molecularly imprinted polymer, may further comprise the steps: the activation of (1) silica gel: it is in 15% the aqueous hydrochloric acid that 5g silica gel is joined 50mL concentration, at 90 ℃ of following stir-activatings, behind the activation 8h, filter, with distilled water thorough washing filter cake, vacuum-drying 30h in vacuum drying oven promptly obtains activatory silica gel at last; (2) silica gel surface chemistry key connects alkylogen: the silica gel after the 5g activation is joined in the four-hole boiling flask of 100mL, adding 50mL organic solvent and 1mL water again is stirring solvent, add 10mL γ-iodine propyl trimethoxy silicane then, react 7h down at 85 ℃, after reaction finishes product is used toluene extracting 30h in Soxhlet extractor, remove unreacted silane coupling agent in the system, vacuum-drying 24h in vacuum drying oven at last obtains the silica gel of iodine propylated; (3) silica gel surface chemistry grafting polyethylene imine PEI: measuring the 55mL mass ratio with graduated cylinder is the four-hole boiling flask that 45% polyethyleneimine: amine aqueous solution places 100mL, take by weighing the silica gel that obtains in the 1g above-mentioned steps (2) again and place four-hole boiling flask, 90 ℃ of back flow reaction 6h, reaction finishes back distilled water flushing product, suction filtration promptly makes sorbing material PEI/SiO after 40 ℃ of vacuum-dryings in vacuum drying oven
2(4) preparation of silica gel molecular imprinted polymer on surface: 1g is adsorbed the template molecule p-methyl phenol to equilibrated graft materials PEI/SiO
2With 6mL1, the aqueous ethanolic solution of 6-dichloro hexane mixes, and the pH that uses the sodium hydroxide solution regulation system is 10, at 40 ℃ of following stirring reaction 5h, after reaction finished, suction filtration was used the hydrochloric acid repetitive scrubbing again, suction filtration, use the distilled water repetitive scrubbing then, suction filtration is till filtrate is neutrality, 40 ℃ of vacuum-dryings in vacuum drying oven then make silica gel surface p-methyl phenol molecular imprinting sorbing material MIP-PEI/SiO
2
Embodiment 4:
A kind of preparation method of silica gel surface phenols molecularly imprinted polymer, may further comprise the steps: the activation of (1) silica gel: it is in 10% the aqueous hydrochloric acid that 7g silica gel is joined 40mL concentration, at 90 ℃ of following stir-activatings, behind the activation 6h, filter, with distilled water thorough washing filter cake, vacuum-drying 27h in vacuum drying oven promptly obtains activatory silica gel at last; (2) silica gel surface chemistry key connects alkylogen: the silica gel after the 7g activation is joined in the four-hole boiling flask of 100mL, adding 45mL toluene and 3mL water again is stirring solvent, add 13mL γ-r-chloropropyl trimethoxyl silane then, react 8h down at 75 ℃, after reaction finishes product is used toluene extracting 27h in Soxhlet extractor, remove unreacted silane coupling agent in the system, vacuum-drying 30h in vacuum drying oven at last obtains the silica gel (CP-SiO of chloropropylation
2); (3) silica gel surface chemistry grafting polyethylene imine PEI: measuring the 54mL mass ratio with graduated cylinder is the four-hole boiling flask that 40% polyethyleneimine: amine aqueous solution places 100mL, take by weighing the silica gel that obtains in the 3g above-mentioned steps (2) again and place four-hole boiling flask, 90 ℃ of back flow reaction 6h, reaction finishes back distilled water flushing product, suction filtration promptly makes sorbing material PEI/SiO after 38 ℃ of vacuum-dryings in vacuum drying oven
2(4) preparation of silica gel molecular imprinted polymer on surface: 3g is adsorbed the template molecule m-nitrophenol to equilibrated graft materials PEI/SiO
2Mix with the aqueous ethanolic solution of 6mL epoxy chloropropane, with the pH of sodium hydroxide solution regulation system 10, at 35 ℃ of following stirring reaction 4h, after reaction finishes, suction filtration, use the hydrochloric acid repetitive scrubbing again, suction filtration is used the distilled water repetitive scrubbing then, suction filtration, till filtrate was neutrality, 37 ℃ of vacuum-dryings in vacuum drying oven then made silica gel surface m-nitrophenol molecular imprinting sorbing material MIP-PEI/SiO
2
Claims (4)
1, a kind of preparation method of silica gel surface phenols molecularly imprinted polymer is characterized in that may further comprise the steps:
(1) activation of silica gel;
(2) silica gel surface chemistry key connects alkylogen: the silica gel after 5～10g activation is joined in the four-hole boiling flask of 100mL, adding 40～60mL organic solvent and 1～5mL water again is stirring solvent, add the halogen-containing silane coupling agent of 10～15mL then, react 6～8h down at 70～80 ℃, after reaction finishes product is used toluene extracting 24～30h in Soxhlet extractor, remove unreacted silane coupling agent in the system, at last vacuum-drying 24～30h in vacuum drying oven;
(3) silica gel surface chemistry grafting polyethylene imine PEI: measuring 50～60mL mass ratio with graduated cylinder is the four-hole boiling flask that 30～50% polyethyleneimine: amine aqueous solution places 100mL, take by weighing the silica gel that obtains in 1～4g above-mentioned steps (2) again and place four-hole boiling flask, 90 ℃ of back flow reaction 5～7h, reaction finishes back distilled water flushing product, suction filtration promptly makes sorbing material PEI/SiO after 34～40 ℃ of vacuum-dryings in vacuum drying oven
2
(4) preparation of silica gel molecular imprinted polymer on surface: 1～4g is adsorbed the template molecule aldehydes matter to equilibrated graft materials PEI/SiO
2Mix with the aqueous ethanolic solution of 5～8mL linking agent, with the pH of sodium hydroxide solution regulation system between 8 to 11, at 20～50 ℃ of following stirring reaction 3～6h, after reaction finishes, suction filtration, use the hydrochloric acid repetitive scrubbing again, suction filtration is used the distilled water repetitive scrubbing then, suction filtration, till filtrate was neutrality, 35～40 ℃ of vacuum-dryings in vacuum drying oven then made silica gel surface phenols molecularly imprinted sorbing material MIP-PEI/SiO
2
2, the preparation method of a kind of silica gel surface phenols molecularly imprinted polymer according to claim 1, it is characterized in that method that silica gel activating adopts is that 5～10g silica gel is joined 30～60mL concentration is in 5%～20% the aqueous hydrochloric acid, at 90 ℃ of following stir-activatings, behind activation 4～8h, filter, with distilled water thorough washing filter cake, vacuum-drying 24～30h in vacuum drying oven promptly obtains activatory silica gel at last.
3, the preparation method of a kind of silica gel surface phenols molecularly imprinted polymer according to claim 1 and 2 is characterized in that described halogen-containing silane coupling agent is any one in γ-r-chloropropyl trimethoxyl silane or γ-bromopropyl Trimethoxy silane or the γ-iodine propyl trimethoxy silicane.
4, the preparation method of a kind of silica gel surface phenols molecularly imprinted polymer according to claim 1 and 2 is characterized in that described linking agent is ethylene glycol diglycidylether or 1,4-dichlorobutane or 1, any one in 6-dichloro hexane or the epoxy chloropropane.
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