CN103614916B - A kind of SPE composite nano-fiber material preparation method - Google Patents
A kind of SPE composite nano-fiber material preparation method Download PDFInfo
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- CN103614916B CN103614916B CN201310590337.8A CN201310590337A CN103614916B CN 103614916 B CN103614916 B CN 103614916B CN 201310590337 A CN201310590337 A CN 201310590337A CN 103614916 B CN103614916 B CN 103614916B
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Abstract
The invention discloses a kind of preparation method of SPE composite nano-fiber material, it is obtained by following steps, 1) sulfonation or carboxylated of nanofiber: band phenyl ring polymer or band phenyl ring polymer and the mixture not with phenyl ring polymer are immersed in the concentrated sulfuric acid by the nanofiber that electrospinning device is obtained and obtain sulfonation nanofiber; Maybe band phenyl ring polymer or band phenyl ring polymer are immersed in the reaction bulb filling phthalic acid anhydride solution with the mixture not with phenyl ring polymer by the nanofiber that electrospinning device obtains, logical purity nitrogen also stirs, obtained carboxylated nanofiber under normal pressure; Twice cleaning is carried out to described sulfonation nanofiber or carboxylated nanofiber; 2) conducting polymer modified nanofiber: get 1) through cleaning after sulfonation nanofiber or carboxylated nanofiber, add pyrroles, thiophene or aniline monomer and oxidant, obtain conducting polymer modified nanofiber at nanofiber surface by home position polymerization reaction.
Description
Technical field
The present invention relates to a kind of nano material for analytical chemistry field, particularly a kind of composite nano fiber SPE material with cation exchange properties.
Background technology
SPE is applied to a lot of field as a kind of Sample Pretreatment Technique, and SPE has a lot of advantage compared with traditional abstraction technique.Solid phase extraction adsorbents is solid-state, is the core of extraction, determines the performance of SPE.In recent years, by testing sample species influence, be sorbent usedly able to fast development.
Nano-fiber solid phase extraction column is the new a kind of solid-phase extraction column for sample pre-treatments using nanofiber as solid phase extraction adsorbents risen.First nano-fiber solid phase extraction column has the advantage of general solid-phase extraction column, as: high sample recovery rate, good reappearance, extraction simple and fast, sample purification is effective, in addition, the skin effect had by means of nanofiber self and small-size effect etc., nano-fiber solid phase extraction column possesses the features such as and adsorptive selectivity higher than general solid-phase extraction column adsorption capacity be good, consumption with organic solvent in sample pretreatment process reduces further, after micro-eluant, eluent makes object be eluted, do not need to volatilize, the steps such as redissolution, improve the efficiency of sample analysis.Nano-fiber solid phase extraction column has very large application prospect by sample pre-treatments field, and also will be very necessary for the research of the nanofiber solid phase extraction adsorbents with different adsorption function.
Based on the above, research and develop a kind of composite nano fiber SPE sorbing material with cation exchange properties and will expand the range of application of nanofiber SPE further, its exploitation is by necessary property.
Summary of the invention
For the above, the invention provides a kind of composite nano fiber SPE material for extracting cationic polar compound.
Nanofiber SPE material provided by the invention by material of main part, there is the functional group of cation exchange properties and the hydrophobic components based on conducting polymer forms.
Described SPE composite nano-fiber material is obtained by following steps, 1) nanofiber is prepared: band phenyl ring polymer or band phenyl ring polymer are obtained nanofiber with the mixture not with phenyl ring polymer by electrospinning device, rear drying for standby, the voltage of electrospinning device is 9 ~ 60kV, pole span 5 ~ 30cm, feeding speed 0.5 ~ 5mL/h; 2) sulfonation or carboxylated of nanofiber: get 1) in dried nanofiber, immerse in the excessive concentrated sulfuric acid, under normal temperature ultrasonic or stir 5 ~ 60min obtain sulfonation nanofiber; Or by 1) in dried nanofiber immerse and fill in the reaction bulb of phthalic acid anhydride solution, logical purity nitrogen also stirs, obtained carboxylated nanofiber under normal pressure; Carry out twice cleaning to described sulfonation nanofiber or carboxylated nanofiber, wherein sulfonate group or carboxylate group provide cation exchange effect; 3) conducting polymer modified nanofiber: get 2) through cleaning after sulfonation nanofiber or carboxylated nanofiber, add the conducting polymer monomer solutions such as pyrroles, thiophene or aniline and oxidant (iron chloride, ammonium persulfate etc.) to carry out home position polymerization reaction and obtain conducting polymer modified nanofiber, clean described conducting polymer modified nanofiber and dry process, wherein conducting polymer provides as hydrophobic effect, π-πconjugation or other special roles etc.
Step 2 in above-mentioned steps) and step 3) can exchange, by step 1) obtained nanofiber is through above-mentioned steps 3) obtain conducting polymer modified nanofiber after process, then by conducting polymer modified nanofiber through above-mentioned steps 2) process, sulfonation or carboxylated process are carried out to conducting polymer modified nanofiber.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 1) in the drying of nanofiber carry out in baking oven, described oven temperature is 30 ~ 100 DEG C.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 2) in twice cleaning comprise, first time cleaning: with ethanol purge; Second time cleaning: clean to cleaning fluid in neutral with a large amount of distilled water.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 3) in by 2) cleaning after sulfonation nanofiber or carboxylated nanofiber put into water, add pyrroles and oxidant respectively, the ratio of pyrroles and oxidant is 1: 1 ~ 1: 10, by containing sulfonation nanofiber or the pyrroles of carboxylated nanofiber and the mixture of oxidant ultrasonic vibration or stir 20 ~ 60min, the obtained cation exchange nanofiber SPE material having modified pyrroles in 30 ~ 80 DEG C of water-baths.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 3) in by 2) cleaning after sulfonation nanofiber or carboxylated nanofiber put into water, add thiophene and oxidant respectively, thiophene and oxidant ratio are 1: 100 ~ 1: 300, by containing sulfonation nanofiber or the thiophene of carboxylated nanofiber and the mixture of oxidant ultrasonic vibration or stir 24 ~ 36h, the obtained cation exchange nanofiber SPE material having modified thiophene in 60 ~ 90 DEG C of water-baths.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 3) in by 2) cleaning after sulfonation nanofiber or carboxylated nanofiber put into aqueous hydrochloric acid solution, add aniline and oxidant respectively, aniline and oxidant ratio are 2: 1 ~ 1: 5, by the mixture ultrasonic vibration of the aniline containing sulfonation nanofiber or carboxylated nanofiber and oxidant or stir 1 ~ 2h, cleaning, the obtained cation exchange nanofiber SPE material having modified polyaniline.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 3) in cleaning be by successively with ethanol, sodium dodecyl sulfate aqueous solution, ethanol, distilled water to described conducting polymer modified nanofiber carry out rinse realization.
Preferably, described SPE composite nano-fiber material preparation method, wherein, step 3) in dry process be realize by the nanofiber after rinsing is placed in 40 ~ 60 DEG C of baking oven inner dryings.
The nanofiber SPE material obtained by SPE composite nano-fiber material preparation method provided by the invention can load into column type, taper or plate-like etc.; Can be used for SPE or other with adsorb, be separated, extract relevant work.Described SPE composite nano-fiber material preparation method step is simple, be easy to operation implements, and success rate is high.
Detailed description of the invention
The present invention is described in further detail below, can implement according to this with reference to description word to make those skilled in the art.
I: the preparation of nanofiber
1) polystyrene (Mw=150,000 ~ 200,000) is dissolved in oxolane and N, in N-2-methylformamide mixed solution, wherein oxolane and N, N-2-methylformamide volume ratio are 6:4 ~ 4:6, and the mass concentration of polystyrene is 15%;
2) inject in the reservoir of electrostatic spinning apparatus by polymer solution, by electrospinning device, polystyrene solution is prepared into polystyrene nano fiber, electrospinning conditions is: voltage 17kV, pole span 20cm, feeding speed 2.0mL/h;
3) nanofiber prepared is stripped down from dash receiver, at 40 ~ 60 DEG C of baking oven inner dryings.
II: the sulfonation of nanofiber
1) get the nanofiber of 1g drying, add 0.2 ~ 0.4L concentrated sulfuric acid, ultrasonic 30min under normal temperature;
2) remove most of sulfuric acid, after 100 ~ 200mL ethanol purge, with a large amount of distilled water, nanofiber is cleaned to neutrality.
III: conducting polymer modified
1) solution prepares: configuration pyrroles's aqueous solution of 40mM and the ferric chloride in aqueous solution of 80mM, be heated to 60 DEG C in a water bath;
2) get the nanofiber after above-mentioned sulfonation, add 0.4 ~ 0.6L pyrroles aqueous solution and 0.4 ~ 0.6L ferric chloride in aqueous solution, after mixing, 60 DEG C of ultrasonic 30min;
3) take out nanofiber, use ethanol, sodium dodecyl sulfate aqueous solution, ethanol, distilled water flushing respectively;
4) nanofiber is placed in 40 ~ 60 DEG C of drying in oven, obtained a kind of cation exchange nanofiber SPE material having modified polypyrrole.
IV: the pre-treatment of Ractopamine in pork
1) getting 5 ~ 8mg above-mentioned nanofiber SPE material loads in nano-fiber solid phase extraction column;
2) grape alditol glucoside enzyme/aryl sulfatase enzymolysis 12h will be added after 2g pork homogenate;
3) with 5% perchloric acid precipitation's albumen, take out supernatant, with sodium hydroxide solution, supernatant pH is adjusted to 8.0, pending;
4) by nano-fiber solid phase extraction column 200 μ L methyl alcohol and the activation of 200 μ L water, pending solution is passed through nano-fiber solid phase extraction column;
5) with after 100 μ L10% methyl alcohol drip washing, by 100 μ L methanol-eluted fractions, machine testing on appropriate eluent is got.
The mark-on extraction recovery of the method is between 83% ~ 98%.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (5)
1. a preparation method for SPE composite nano-fiber material, is characterized in that, is obtained by following steps,
1) sulfonation or carboxylated of nanofiber: band phenyl ring polymer or band phenyl ring polymer are carried out sulfonation with the nanofiber concentrated sulfuric acid do not prepared with the mixture of phenyl ring polymer and obtains sulfonation nanofiber; Maybe immerse in the reaction bulb filling phthalic acid anhydride solution by band phenyl ring polymer or band phenyl ring polymer with the nanofiber do not prepared with the mixture of phenyl ring polymer, logical purity nitrogen also stirs, obtained carboxylated nanofiber under normal pressure; Twice cleaning is carried out to described sulfonation nanofiber or carboxylated nanofiber;
2) conducting polymer modified nanofiber: get 1) through cleaning after sulfonation nanofiber or carboxylated nanofiber, add pyrroles, thiophene or aniline monomer and oxidant, described oxidant is ammonium persulfate, obtain conducting polymer modified nanofiber at nanofiber surface by home position polymerization reaction, described conducting polymer modified nanofiber is cleaned and dry process;
Wherein, step 2) in by cleaning after sulfonation nanofiber or carboxylated nanofiber put into water, add pyrrole monomer and oxidant respectively, the ratio of pyrrole monomer and oxidant is 1:1 ~ 1:10, by containing sulfonation nanofiber or the pyrroles of carboxylated nanofiber and the mixture of oxidant ultrasonic vibration or stir 20 ~ 60min, the obtained cation exchange nanofiber SPE material having modified pyrroles in 30 ~ 80 DEG C of water-baths;
Step 2) the sulfonation nanofiber after cleaning or carboxylated nanofiber are put into water, add the thiophene and oxidant that have been preheated to 60 ~ 90 DEG C respectively, thiophene and oxidant ratio are 1:100 ~ 1:300, by containing sulfonation nanofiber or the thiophene of carboxylated nanofiber and the mixture of oxidant ultrasonic vibration or stir 24 ~ 36h, the obtained cation exchange nanofiber SPE material having modified thiophene in 60 ~ 90 DEG C of water-baths;
Step 2) the sulfonation nanofiber after cleaning or carboxylated nanofiber are put into aqueous hydrochloric acid solution, add aniline and oxidant respectively, aniline and oxidant ratio are 2:1 ~ 1:5, by the mixture ultrasonic vibration of the aniline containing sulfonation nanofiber or carboxylated nanofiber and oxidant or stir 1 ~ 2h, cleaning, the obtained cation exchange nanofiber SPE material having modified polyaniline.
2. SPE composite nano-fiber material preparation method as claimed in claim 1, it is characterized in that, described band phenyl ring polymer or band phenyl ring polymer are adopt electrospinning device to obtain with the nanofiber do not prepared with the mixture of phenyl ring polymer, described electrospinning device voltage is 9 ~ 60kV, pole span 5 ~ 30cm, feeding speed 0.5 ~ 5mL/h, obtained nanofiber is at 40 ~ 60 DEG C of baking oven inner dryings.
3. SPE composite nano-fiber material preparation method as claimed in claim 1, is characterized in that, step 2) in twice cleaning comprise,
First time cleaning: with ethanol purge;
Second time cleaning: clean to cleaning fluid in neutral with a large amount of distilled water.
4. SPE composite nano-fiber material preparation method as claimed in claim 1, it is characterized in that, step 2) described in cleaning be by successively with ethanol, sodium dodecyl sulfate aqueous solution, ethanol, distilled water to described conducting polymer modified nanofiber carry out rinse realization.
5. SPE composite nano-fiber material preparation method as claimed in claim 1, is characterized in that, step 2) described in dry process be realize by the nanofiber after rinsing is placed in 40 ~ 60 DEG C of baking oven inner dryings.
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| CN104020167B (en) * | 2014-06-19 | 2016-08-17 | 天津医科大学 | A kind of use the method for iodine in polypyrrole nanofibers film detection sample |
| CN105080515B (en) * | 2015-09-02 | 2017-08-22 | 浙江省农业科学院 | MIP SPME extracting fibers and extraction platform and application |
| CN107308998B (en) * | 2017-06-23 | 2019-06-25 | 延边大学 | A kind of micro-fluidic carbon nano-fiber size exclusion chromatography separation method of magnetic field auxiliary |
| CN109126751A (en) * | 2018-09-07 | 2019-01-04 | 南阳理工学院 | A kind of preparation method of toxic gas adsorbing material |
| CN110567786B (en) * | 2019-08-06 | 2020-09-29 | 中南大学 | Spatial resolution enrichment purification sampling method for mass spectrometry imaging |
| CN110652749B (en) * | 2019-09-29 | 2021-09-24 | 华中师范大学 | Composite nanofiber online micro solid-phase extraction column and preparation method thereof |
| CN117585987B (en) * | 2024-01-18 | 2024-03-19 | 河北国亮新材料股份有限公司 | Tundish coating material and preparation method thereof |
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| CN102758264A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院化学研究所 | Polymer nanofiber and preparation method and application of functional/hybrid material thereof |
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| CN101497034A (en) * | 2009-01-05 | 2009-08-05 | 东南大学 | Solid phase extraction method based on nylon nano fiber film and extractor |
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