CN108421542B - Application of liquid metal microspheres as pore-forming agent in preparation of monolithic column - Google Patents
Application of liquid metal microspheres as pore-forming agent in preparation of monolithic column Download PDFInfo
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- CN108421542B CN108421542B CN201810240781.XA CN201810240781A CN108421542B CN 108421542 B CN108421542 B CN 108421542B CN 201810240781 A CN201810240781 A CN 201810240781A CN 108421542 B CN108421542 B CN 108421542B
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Abstract
The invention discloses application of liquid metal microspheres as a pore-foaming agent in preparation of an integral column. The method is a simple, convenient and efficient method for preparing the liquid drop with the controllable diameter by taking the surfactant as the surface coating layer of the metal liquid drop and utilizing ultrasonic crushing, and the liquid drop is applied to the macromolecule porous monolithic column polymerization of adsorption separation analysis to be used as a green pore-foaming agent to replace the conventional toxic and high-pollution organic solvent. Meanwhile, after the high molecular polymer is polymerized, the liquid metal microsphere pore-foaming agent is washed out under the action of high-pressure hot water and then recycled, so that adsorption holes and diffusion channels with the sizes matched with the molecular sizes of adsorption separation objects are obtained in the high molecular porous material. The preparation method of the adsorption separation high polymer porous material which is green and has controllable aperture and porosity is achieved. The invention replaces the conventional toxic and high-pollution organic solvent pore-forming agent with liquid metal liquid drops with nanometer and micrometer diameters, and realizes the control of the aperture of the whole column by controlling the particle size of the liquid metal microspheres. The prepared monolithic column has uniform structure and good permeability.
Description
Technical Field
The invention relates to preparation and application of a polymer monolithic column, in particular to application of liquid metal microspheres as a pore-foaming agent in preparation of the monolithic column.
Background
The polymer monolithic column is used as a novel material, and is prepared by injecting a prepolymerization mixed solution (comprising an organic functional monomer, a cross-linking agent and a pore-forming agent) into an empty chromatographic column or a capillary column, thermally or photo-initiating a material with a continuous bed structure polymerized in situ in a tube, and then removing the pore-forming agent and unreacted monomers by adopting a proper solvent and being driven by a mechanical pump or electroosmotic flow. The prepared and synthesized monolithic column has the advantages of good permeability, high mass transfer speed, high separation efficiency and easy modification. In addition, it also has the character of perfusion chromatography, i.e. the chromatographic column has both flow-through pores (close to 1 μm) for the mobile phase and mesopores (tens of nanometers) for facilitating mass transfer of solutes, and the stability of the chromatographic column is very good, so the whole column is also known as a fourth generation of chromatographic packing after polysaccharide, cross-linking and coating, and monodispersion. In the process of developing the monolithic column, the optimization of polymerization reaction conditions plays a decisive role, once the polymerization reaction conditions are optimized and selected, the success rate of the prepared chromatographic column can reach 100 percent, so that the successful pore-foaming agent is important for preparing the monolithic column with good performance.
At present, the types of pore-foaming agent systems used for preparing capillary monolithic columns are relatively few, and most of reported documents use toxic and high-pollution organic solvents (such as toluene, isooctane, n-hexanol, 1, 4-butanediol and the like) as pore-foaming agents. Therefore, the development of low-toxicity green pore-foaming agents is a new development direction for preparing the macromolecular porous capillary monolithic column for adsorption separation analysis.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the application of liquid metal microspheres as a pore-foaming agent in preparing an integral column. The low melting liquid metal is an amorphous, flowable liquid metal. Preparing liquid metal into functional microsphere liquid drops with submicron diameters and then applying the functional microsphere liquid drops to other related fields, such as preparation of flexible electrodes or conductor materials by filling monodisperse nano or micro microspheres into microchannels, fibers or porous structures; the liquid metal and other soft or elastic materials are blended to prepare flexible composite materials and the like. Meanwhile, the low-melting-point liquid metal has the characteristics of high thermal conductivity, low viscosity, easiness in realization of a melting and solidifying process, recyclability and the like, so that the low-melting-point liquid metal has unique advantages in application of the monolithic column pore-foaming agent.
The technical scheme of the invention is as follows: the liquid metal microsphere is used as a pore-forming agent in the preparation of an integral column.
Further improvements of the invention include:
the liquid metal is gallium or gallium-indium liquid alloy.
The preparation method of the monolithic column comprises the following steps: preparing liquid metal microspheres, wherein methacrylate is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, and the molar ratio is 1: 4-1: 6; adding liquid metal microspheres accounting for 30-60% of the total volume of the functional monomer and the cross-linking agent, and adding a photoinitiator 1800 accounting for 1-3% of the mass of the functional monomer to prepare the polyacrylate capillary monolithic column. Introducing nitrogen into the mixed solution for 15 minutes before polymerization reaction so as to remove dissolved oxygen in the prepolymerization solution; and then the mixed solution is injected into a capillary and is placed in a hot water bath at the temperature of 60 ℃ for 12 hours to generate the in-situ polymerization reaction of the free radicals.
The methacrylate is 2-methacrylic acid, butyl methacrylate, isobutyl methacrylate and/or hydroxyethyl methacrylate as a functional monomer.
The preparation method of the liquid metal microsphere comprises the following steps: liquid metal and a surfactant are added into dispersed phase isopropanol according to the mass ratio of 1:0.2:1, performing ultrasonic treatment to obtain dispersed liquid metal droplets, performing ultrahigh-speed centrifugation (25000rpm) on the prepared dispersed liquid metal droplets for 15 minutes, extracting and removing supernatant, reserving bottom sediment, adding isopropanol, performing centrifugation and supernatant removal under the conditions, repeating the operation for 3 times to remove redundant surfactant, performing low-temperature (-40 ℃) freeze drying to obtain liquid metal microsphere powder, and placing the liquid metal microsphere powder in a low-temperature refrigerator for later use; the surfactant is wrapped on the surface of the liquid metal drop, so that the surface tension of the liquid metal can be obviously reduced, and the formed metal drops can be regularly arranged on the surface of the solution in an oriented mode. The liquid metal droplet diameter is controlled by the four factors of the amount of the surfactant, the temperature, the ultrasonic power and the time.
The surfactant is tween 80, span 80, triton 100, hexadecyl trimethyl ammonium bromide and/or lauryl sodium sulfate.
The temperature during ultrasonic treatment is 15-50 ℃; the ultrasonic power is 50-200W.
The diameter of the liquid metal microsphere is 250 nm-1200 nm.
The preparation method of the monolithic column also comprises the following steps of removing liquid metal microspheres, and specifically comprises the steps of taking the obtained monolithic column out, connecting the monolithic column to a high-pressure infusion pump, controlling the temperature to be 30 ℃, washing the monolithic column for 6 hours by using a conductive aqueous solution containing a salt medium at the flow rate of 0.2m L/min to remove the liquid metal microspheres, and then washing by using methanol to remove unreacted monomers in the monolithic column to obtain the capillary monolithic column with controllable aperture and porosity.
The invention discloses a simple, convenient and efficient method for preparing droplets with controllable diameters by taking a surfactant as a surface coating layer of metal droplets, which is applied to macromolecular porous monolithic column polymerization for adsorption separation analysis as a green pore-forming agent to replace a conventional toxic and highly-polluted organic solvent. And simultaneously, after the polymerization of the high molecular polymer is finished, the liquid metal pore-foaming agent is washed out under the action of high-pressure hot water and then recycled, so that adsorption holes and diffusion channels which are matched with the molecular size of an adsorption separation object are obtained in the high molecular porous material. The preparation method of the adsorption separation high polymer porous material which is green and has controllable aperture and porosity is achieved.
The method for preparing the monolithic column by using the submicron liquid metal microspheres as the pore-forming agent replaces the conventional toxic and high-pollution organic solvent pore-forming agent with liquid metal liquid drops with nanometer and micron diameters, and realizes the control of the pore diameter of the monolithic column by controlling the particle diameter of the liquid metal microspheres. The prepared monolithic column has uniform structure and good permeability. The invention solves the technical problems that the particle size control of the liquid metal ball and the treatment and storage after the preparation are not solved in the prior art.
Drawings
FIG. 1 is a transmission scanning electron microscope image of a liquid metal microsphere prepared in example 1 according to the present invention.
FIG. 2 is a scanning electron micrograph of a monolith prepared in example 1 according to the present invention.
FIG. 3 chromatographic retention of the compounds of example 1 of the invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Liquid metal gallium is used as a pore-foaming agent, 0.5g of gallium and 0.1g of Tween 80 are added into 5m L of isopropanol, the temperature is controlled to be 20 ℃, the ultrasonic power is 150W, and ultrasonic treatment is carried out for 30 minutes to prepare dispersed liquid metal droplets with the particle size range of 250 nm-1200 nm.
And (3) carrying out ultra-high speed centrifugation (25000rpm) on the prepared dispersed liquid metal droplets for 15 minutes, then extracting and removing supernatant, retaining bottom sediments, adding 10m L isopropanol, centrifuging and removing the supernatant under the conditions, repeating the operation for 3 times to remove redundant surfactant, carrying out low-temperature freeze drying (-40 ℃) to obtain liquid metal microsphere powder, and placing the liquid metal microsphere powder in a low-temperature refrigerator (-10 ℃) for storage.
Methacrylic acid is taken as a functional monomer, ethylene glycol dimethacrylate is taken as a cross-linking agent, and the molar ratio is 1: 4. Adding liquid metal microspheres accounting for 50% of the total volume of the functional monomer and the cross-linking agent, and adding a photoinitiator 1800 accounting for 2% of the total mass of the functional monomer and the cross-linking agent to prepare the monolithic column. Introducing nitrogen into the mixed solution for 15 minutes before polymerization reaction so as to remove dissolved oxygen in the prepolymerization solution; and then injecting the mixed solution into a capillary tube, and polymerizing for 20min under ultraviolet light to obtain the monolithic column.
Connecting two ends of the prepared monolithic column with PEEK three-way connectors, wherein one end of the PEEK is connected to a high-pressure infusion pump, the other end of the PEEK is communicated with a waste liquid pipe, inserting platinum wire electrodes into one port of each of the PEEK three-way connectors at the two ends, switching on a direct-current power supply, controlling the voltage to be 60V and the current to be 0.03 mA., controlling the temperatures of a flushing mobile phase and the monolithic column to be 30 ℃, flushing the monolithic column for 6 hours at the flow rate of 0.2m L/min by using a conductive aqueous solution containing a salt medium to remove liquid metal microspheres, then directly flushing for 6 hours at the flow rate of 0.2m L/min by using methanol after the power supply is stopped to remove unreacted monomers in the monolithic column, and obtaining the capillary monolithic column with controllable aperture and porosity-15m of a sample solution of L (containing tetracycline, oxytetracycline, doxycycline and chlortetracycline each 20.0. mu.g L)-1) Flowing through a capillary column; after the enrichment is finished, controlling the high pressureThe flow rate of the pump is 0.03m L min-10.1m L of methanol was passed through a capillary column and the methanol eluate was collected for analysis by HP L C/UV.
Conditions of liquid chromatography
Agilent 1260L C chromatography system C18 column (5 μm, 250mm × 4.6.6 mm i.d.) mobile phase acetonitrile (a) and water (B), isocratic elution (a: B ═ 35:65) flow rate 1.0m L min-1The sample size is 10 mu L with the wavelength of 355 nm.
Under the guidance of the present embodiment, those skilled in the art can reproduce the present technical solution accurately according to other process parameters described in the description, and therefore, in order to save the examination resources, other embodiments are not listed again.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The application of the liquid metal microspheres as a pore-forming agent in preparing an integral column comprises the following steps: mixing liquid metal and a surfactant in dispersed phase isopropanol according to the mass ratio of 1:0.2:1, performing ultrasonic treatment to obtain dispersed liquid metal droplets, performing ultrahigh-speed centrifugation on the prepared dispersed liquid metal droplets for 15 minutes, extracting and removing supernatant, retaining bottom sediment, adding isopropanol, performing centrifugation and supernatant removal under the conditions for 3 times to remove redundant surfactant, and performing low-temperature freeze drying to obtain liquid metal microsphere powder; the surfactant is wrapped on the surface of the liquid metal drop, so that the surface tension of the liquid metal can be obviously reduced, and the formed metal drops can be regularly arranged on the surface of the solution in an oriented manner; the temperature during ultrasonic treatment is 15-50 ℃; the ultrasonic power is 50-200W; the preparation method of the monolithic column comprises the following steps: preparing liquid metal microspheres, wherein methacrylate is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, and the molar ratio is 1: 4-1: 6; adding liquid metal microspheres accounting for 30-60% of the total volume of the functional monomer and the cross-linking agent, and adding a photoinitiator accounting for 1-3% of the mass of the functional monomer to prepare a polyacrylate capillary monolithic column; the preparation method of the monolithic column also comprises the step of removing the liquid metal microspheres, and the specific steps are as follows: connecting two ends of the obtained integral column with PEEK three-way connectors, wherein one end of the PEEK is connected to a high-pressure infusion pump, and the other end of the PEEK is communicated with a waste liquid pipe; platinum wire electrodes are respectively inserted into one port of the PEEK tee joints at the two ends, a direct current power supply is connected, the voltage is controlled to be 30V-120V, and the current is controlled to be 0.01 mA-0.5 mA; simultaneously controlling the temperature of the washing mobile phase and the temperature of the monolithic column to be 25-35 ℃, and washing the monolithic column by using a conductive aqueous solution containing a salt medium to remove the liquid metal microspheres; and (3) directly washing with methanol after the power supply is stopped to remove unreacted monomers in the monolithic column to obtain the organic polymer monolithic chromatographic column with controllable pore diameter and porosity.
2. Use according to claim 1, wherein the liquid metal is gallium or a gallium-indium liquid alloy.
3. Use according to claim 1, characterized in that the functional monomer is butyl methacrylate, isobutyl methacrylate or hydroxyethyl methacrylate.
4. Use according to claim 1, wherein the surfactant is tween 80, span 80, cetyl trimethylammonium bromide or sodium lauryl sulphate.
5. The use according to claim 1, wherein the liquid metal microspheres have a diameter of 250nm to 1200 nm.
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| CN101073714A (en) * | 2007-04-06 | 2007-11-21 | 武汉大学 | Method for producing solid-phase microextraction capillaries |
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| DE102008050588A1 (en) * | 2008-10-09 | 2010-04-15 | Martin-Luther-Universität Halle-Wittenberg | Immobilized monomeric avidin monolithic column for enrichment and identification of biotinylated species |
| CN102500344A (en) * | 2011-10-27 | 2012-06-20 | 西北工业大学 | Preparation method for non-polar polymer monolithic columns |
| CN103068939A (en) * | 2010-08-26 | 2013-04-24 | 原子能和替代能源委员会 | Liquid metal emulsion |
| CN103433008A (en) * | 2013-09-13 | 2013-12-11 | 河南科技学院 | Hollow-fiber-film-coated molecular imprinting integral adsorption rod, as well as preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101073714A (en) * | 2007-04-06 | 2007-11-21 | 武汉大学 | Method for producing solid-phase microextraction capillaries |
| CN101246150A (en) * | 2008-03-28 | 2008-08-20 | 南开大学 | Tsiklomitsin molecular engram integral column preparation method |
| DE102008050588A1 (en) * | 2008-10-09 | 2010-04-15 | Martin-Luther-Universität Halle-Wittenberg | Immobilized monomeric avidin monolithic column for enrichment and identification of biotinylated species |
| CN103068939A (en) * | 2010-08-26 | 2013-04-24 | 原子能和替代能源委员会 | Liquid metal emulsion |
| CN102500344A (en) * | 2011-10-27 | 2012-06-20 | 西北工业大学 | Preparation method for non-polar polymer monolithic columns |
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