CN103170162B - Preparation method of super-macroporous capillary monolithic column by taking polystyrene as pore-foaming agent - Google Patents
Preparation method of super-macroporous capillary monolithic column by taking polystyrene as pore-foaming agent Download PDFInfo
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- CN103170162B CN103170162B CN201310133466.4A CN201310133466A CN103170162B CN 103170162 B CN103170162 B CN 103170162B CN 201310133466 A CN201310133466 A CN 201310133466A CN 103170162 B CN103170162 B CN 103170162B
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Abstract
The method relates to a method for preparing an organic polymer, namely a capillary monolithic column and controlling the structure of the polymer through an in-situ polymerization method. The method comprises the following steps of: taking polystyrene, isooctane and dimethyl sulfoxide dissolved in tetrahydrofuran as pore-foaming agents, and when the content of the polystyrene in the tetrahydrofuran is 40mg/ml and the molecular weight of the polystyrene in the tetrahydrofuran is 350, 000g/mol, the super-macroporous network structures which are interconnected with one another can be seen by a scanning electron microscope. The method has the advantages of being simple in synthetic method and short in reaction time; and the scanning electron microscope experiment on the capillary monolithic column obtained by the method proves that the monolithic column structure of the polymer is highly networked, the bore diameter of the polymer can reach 5-10 microns, and the polymer has good permeability.
Description
Technical field
The present invention relates to a kind of preparation method of the super big hole organic polymer capillary monolithic column taking polystyrene as pore-foaming agent.
Background technology
Capillary chromatographic column can be divided into three types: capillary packed column, capillary open tubular column and capillary monolithic column.Packed column must be prepared plunger, brings thus plunger effect, may cause pillar in running to be scrapped.Though open tubular column without sealing problem, can obtain higher post effect, its compare little, sample capacity is low, detection difficult, be also subject to certain restrictions.The difficulty that capillary chromatographic column runs into has technically been impelled the development of other capillary column technologies of preparing.Capillary monolithic column prepared by in-situ polymerization is one of them.So-called integral post is a kind of fixing phase of continuous bed of carrying out in-situ polymerization with organic or inorganic polymerization in chromatographic column.This chromatographic column preparation method is simple, can fix the various possible effect groups of middle introducing mutually in the time of polymerization in the past, therefore has very changeable flexibility.The solid chromatography column simultaneously making with in-situ polymerization has better porous and permeability than the chromatographic column of conventional filling, has the feature of perfusion chromatography.In addition, in capillary, use monolithic chromatogram column technology can avoid the making of plunger, reduce the bubble formation causing due to plunger.
Selecting polystyrene is due to its suitable physicochemical property, as a kind of linear oligomer, it does not dissolve each other with monomer and crosslinking agent, therefore, use the polystyrene that is dissolved in oxolane as pore-foaming agent, wash-out leave the pore structure of mutual perforation comparatively easily in preparation process.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the super big hole capillary monolithic column taking polystyrene as pore-foaming agent, adopt situ aggregation method that prepolymerization mixed solution is directly injected into and in capillary column, prepares continuous clavate polymer, obtain having the cancellated capillary monolithic column of super big hole, aperture can reach 5-10 μ m, and the method preparation process is simple simultaneously, and the reaction time is shorter, the organic reagent consuming is less, column permeability is good, has avoided loaded down with trivial details dress post formality, can be directly used in analysis.
The preparation method of a kind of super big hole capillary monolithic column taking polystyrene as pore-foaming agent of the present invention, adopts situ aggregation method preparation, specifically comprises the following steps:
1) by mass percent monomer methacrylic acid 1.12%, monomer butyl methacrylate 8.68%-8.72%, initator azodiisobutyronitrile 1.29%-1.30%, crosslinking agent GDMA 2.56%-2.58%, being dissolved in pore-foaming agent is the polystyrene tetrahydrofuran solution of isooctane 11.84%-13.08%, dimethyl sulfoxide (DMSO) 19.63%-19.54% and 53.57%-54.97%, and wherein polystyrene mass percent is 2.31%-2.36%; Ultrasonic 20 minutes of mixed solution, makes it even, and clarification, then transfers in clean capillary column, two ends is sealed and coated vacuum grease sealing with rubber, in the thermostat water bath of 53 DEG C of temperature, reacts 3 hours;
2) capillary column taken out and be connected on syringe and rinse with hand push pump with tube connector, first rinsing with oxolane, to remove pore-foaming agent residual in integral post, rinse with acetonitrile afterwards, remove oxolane, flushing liquor cumulative volume is 4.5 ml, can obtain super big hole capillary monolithic column.
The concentration that pore-foaming agent polystyrene in step 1) is dissolved in tetrahydrofuran solution is 40 mg/ml, and the molecular weight of polystyrene is 350,000 g/mol.
Capillary column in step 1) is 100 μ m I.D..
The preparation method of the super big hole capillary monolithic column taking polystyrene as pore-foaming agent of the present invention, the method adopts the synthetic super big hole organic polymer capillary monolithic column taking polystyrene as pore-foaming agent of in-situ polymerization first, preparation process is simple, easily operation, avoid complicated dress post program, the capillary monolithic column of preparation has the super big hole structure of mutual perforation, has good permeability.
The present invention adopts design by experiment, finds the optimum pore-foaming agent proportioning of the synthetic super big hole capillary monolithic column taking polystyrene as pore-foaming agent; Be the ratio of polystyrene tetrahydrofuran solution, isooctane and dimethyl sulfoxide (DMSO), prepare super big hole capillary monolithic column.
Brief description of the drawings
Fig. 1 is integral post scanning electron microscope (SEM) photograph prepared by the present invention.
Fig. 2 is that the present invention increases capillary monolithic column scanning electron microscope (SEM) photograph prepared by isooctane content.
Detailed description of the invention
Below in conjunction with specific embodiment, further elaborate the present invention.
Embodiment 1
The preparation of the super big hole capillary monolithic column taking polystyrene as pore-foaming agent and ESEM experiment.
Utilize situ aggregation method synthetizing ultramacropore capillary monolithic column, through processing and under suitable condition, observing its architectural feature with ESEM instrument, synthetic reaction condition and processing method are as follows:
Situ aggregation method is prepared super big hole capillary monolithic column:
A, control total liquor capacity and be less than 1.5ml, by the mass number of super big hole capillary monolithic column, accurately take mass percent monomer methacrylic acid 1.12%, monomer butyl methacrylate 8.68%, initator azodiisobutyronitrile 1.29%, crosslinking agent GDMA 2.56%, being dissolved in pore-foaming agent is the polystyrene tetrahydrofuran solution of isooctane 11.84%, dimethyl sulfoxide (DMSO) 19.54% and 54.97%, wherein polystyrene use molecular weight is 350,000g/mol and mass percent are 2.36%, i.e. the polystyrene tetrahydrofuran solution of 40mg/ml.Ultrasonic 20 minutes of mixed solution, makes it even, and then clarification is transferred in clean capillary (preprocess method is processed clean routinely) post, two ends is sealed and coated vacuum grease sealing with rubber, in the thermostat water bath of 53 DEG C of temperature, reacts 3 hours;
B, capillary column take out and are connected on syringe and rinse with hand push pump with tube connector, first rinse with oxolane, to remove pore-foaming agent residual in integral post, then rinse with acetonitrile, remove oxolane, flushing liquor cumulative volume is 4.5 ml, can obtain super big hole capillary monolithic column.
Characterize the physical aspect of capillary monolithic column with scanning electron microscope (SEM) photograph, quartz capillary column sample is cut into the long fragment of 2-3 mm, is fixed in speciality aluminum groove, after sample is gold-plated, obtains picture.All scanning electron microscope images are obtained under 15 kv, 60 mA conditions by Shimadzu SS-550 SEM.
Result shows, use 40ml/ml, the synthetic capillary monolithic column of polystyrene tetrahydrofuran solution of 350,000g/mol molecular weight has the super big hole network structure of mutual perforation, network structure is comparatively intensive, contains the super big hole (Fig. 1) of aperture at 5-10 micron.
Embodiment 2
For investigating isooctane and the structure influence of polystyrene tetrahydrofuran solution ratio to capillary monolithic column in pore-foaming agent, synthesize increase isooctane content, reduce the capillary monolithic column of polystyrene tetrahydrofuran solution content, concrete operation step is as follows:
Control total liquor capacity and be less than 1.5ml, by the mass number of super big hole capillary monolithic column, accurately take mass percent monomer methacrylic acid 1.12%, monomer butyl methacrylate 8.72%, initator azodiisobutyronitrile 1.30%, crosslinking agent GDMA 2.58%, being dissolved in pore-foaming agent is the polystyrene tetrahydrofuran solution of isooctane 13.08%, dimethyl sulfoxide (DMSO) 19.63% and 53.57%, wherein polystyrene use molecular weight is 350,000g/mol and mass percent are 2.31%, i.e. the polystyrene tetrahydrofuran solution of 40mg/ml.By the identical method of embodiment 1 and the synthetic integral post of experiment condition.Polymerization completes the method flushing pillar identical with embodiment 1.
ESEM experiment condition is with embodiment 1, and result shows, increases isooctane content, reduce the capillary monolithic column that polystyrene content of tetrahydrofuran forms, have the network structure of mutual perforation, network structure is comparatively loose, contains the super big hole (Fig. 2) of aperture at 5-10 micron.
Claims (4)
1. a preparation method for the super big hole organic polymer capillary monolithic column taking polystyrene as pore-foaming agent, adopts situ aggregation method preparation, it is characterized in that comprising the following steps:
1) by mass percent monomer methacrylic acid 1.12%, monomer butyl methacrylate 8.68%-8.72%, initator azodiisobutyronitrile 1.29%-1.30%, crosslinking agent GDMA 2.56%-2.58%, being dissolved in pore-foaming agent is the polystyrene tetrahydrofuran solution of isooctane 11.84%-13.08%, dimethyl sulfoxide (DMSO) 19.63%-19.54% and 53.57%-54.97%, and wherein polystyrene mass percent is 2.31%-2.36%; Ultrasonic 20 minutes of mixed solution, makes it even, and clarification, then transfers in clean capillary column, two ends is sealed and coated vacuum grease sealing with rubber, in the thermostat water bath of 53 DEG C of temperature, reacts 3 hours;
2) capillary column taken out and be connected on syringe and rinse with hand push pump with tube connector, first rinsing with oxolane, to remove pore-foaming agent residual in integral post, rinse with acetonitrile afterwards, remove oxolane, flushing liquor cumulative volume is 4.5 ml, can obtain super big hole capillary monolithic column.
2. method according to claim 1, is characterized in that the concentration that the pore-foaming agent polystyrene in step 1) is dissolved in tetrahydrofuran solution is 40 mg/ml, and the molecular weight of polystyrene is 350,000 g/mol.
3. method according to claim 1, is characterized in that the capillary column in step 1) is 100 μ m I.D..
4. what method claimed in claim 1 obtained is organic polymer capillary monolithic column.
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| CN104941252B (en) * | 2014-03-26 | 2017-02-08 | 中国科学院大连化学物理研究所 | Organic-inorganic hybrid monolithic column as well as preparation and application thereof |
| CN104289207B (en) * | 2014-09-28 | 2016-03-30 | 天津医科大学 | A kind of chiral molecules prepares the method for liquid crystal molecule trace integral post as adulterant |
| CN107255683A (en) * | 2017-07-05 | 2017-10-17 | 中国人民解放军63605部队 | A kind of hydrazine propellant analysis filling column preparation method |
| CN108786763A (en) * | 2018-06-11 | 2018-11-13 | 天津医科大学 | The preparation method of the gold nanorods doping integral post of mesoporous silicon oxide cladding |
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| US20050155933A1 (en) * | 2004-01-16 | 2005-07-21 | Archidex | Wallless monolith columns for chromatography |
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| US6573307B1 (en) * | 1998-06-11 | 2003-06-03 | Prometic Biosciences, Inc. | Process for making fluorinated polymer adsorbent particles |
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| CN102883813A (en) * | 2010-02-26 | 2013-01-16 | 迪奥尼克斯公司 | Gh capacity ion chromatography stationary phases and method of forming |
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