CN108421542A - Application of the liquid metal microballoon as pore-foaming agent in preparing integral post - Google Patents
Application of the liquid metal microballoon as pore-foaming agent in preparing integral post Download PDFInfo
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- CN108421542A CN108421542A CN201810240781.XA CN201810240781A CN108421542A CN 108421542 A CN108421542 A CN 108421542A CN 201810240781 A CN201810240781 A CN 201810240781A CN 108421542 A CN108421542 A CN 108421542A
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- liquid metal
- integral post
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing Of Micro-Capsules (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
Application the invention discloses liquid metal microballoon as pore-foaming agent in preparing integral post.It is a kind of simple and effective using surfactant as molten drop surface coating layer, the controllable diameter droplet method prepared using ultrasonication, and it is applied in the high-molecular porous integral post polymerization of adsorbing separation analysis the organic solvent that conventional toxic high pollution is substituted as green pore-foaming agent.It is recycled after simultaneously again being developed liquid metal microsphere pore-forming agent by the effect of high-pressure water heating after high molecular polymer polymerize, to obtain possessing the absorption hole to match with adsorbing separation subject molecule size and diffusion admittance in high-molecular porous material.Reach green, controllable bore diameter and porosity the high-molecular porous material preparation method of adsorbing separation.The present invention, instead of the organic solvent pore-foaming agent of conventional toxic high pollution, the control to integral post aperture is realized by the control of liquid metal microspherulite diameter with the liquid metal droplet of nanometer and micron diameter.Prepare gained whole rod structure is uniform, permeability is good.
Description
Technical field
The present invention relates to the preparation of polyalcohol integral pole and applications, and in particular to liquid metal microballoon is being made as pore-foaming agent
Application in standby integral post.
Background technology
Polyalcohol integral pole is by prepolymerization mixed solution (including organic function monomer, crosslinking as a kind of new material
Agent and pore-foaming agent) it is injected into empty chromatographic column or capillary column, pass through thermal initiation or the tool of the light-initiated in-situ polymerization in pipe
There is the material of continuous bed structure, then removes pore-foaming agent and unreacted using suitable solvent and by mechanical pump or electroosmotic flow driving
Monomer.The integral post for preparing synthesis has the advantages that good penetrability, mass transfer velocity are fast, separative efficiency is high and easily modified.This
It is outer it also have the characteristics that perfusion chromatography, i.e., in chromatographic column the recirculation hole (close to 1 μm) of existing mobile phase and have convenient for solute into
The mesoporous (tens nanometers) of row mass transfer, and the stability of chromatographic column is fine, therefore integral post is also known as after polysaccharide, hands over
Connection and forth generation chromatograph packing material coated, after monodisperse.During integral post is developed, the optimization of polymeric reaction condition rises
Conclusive effect, once polymeric reaction condition optimization is selected, the chromatographic column success rate of preparation is developed up to 100%
Successful pore-foaming agent is most important to the good integral post of processability.
Currently, the pore-foaming agent system type prepared used in capillary monolithic column is also fewer, the document reported, mostly with
Toxic, high pollution organic solvent (such as toluene, isooctane, n-hexyl alcohol, 1,4-butanediol) is pore-foaming agent.Therefore, it develops low
Poison, green pore-foaming agent are a kind of new developing direction of high-molecular porous capillary monolithic column for preparing adsorbing separation analysis.
Invention content
In order to solve the deficiencies in the prior art, the present invention provides liquid metal microballoon as pore-foaming agent in preparation integral post
In application.Low melting point liquid metal be a kind of indefinite form, flowable liquids metal.It prepared by liquid metal straight at sub-micron
The research that the functional microsphere drop of diameter is used further to other related fields is concerned, such as by mono-dispersed nano or micron microballoon
It is filled into and prepares flexible electrode or conductor material in microchannel, fiber or porous structure；Liquid metal and other soft or bullets
Property material blending prepares flexible composite etc..Meanwhile low melting point liquid metal thermal conductivity is big, viscosity is low, Melting And Solidification process
The features such as easy to implement, recoverable, it is made to show unique advantage in the application of integral post pore-foaming agent.
The technical scheme is that：Application of the liquid metal microballoon as pore-foaming agent in preparing integral post.
Further improvement of the present invention includes：
The liquid metal is gallium or gallium-indium liquid alloy.
The preparation method of the integral post is as follows：Liquid metallic microspheres are prepared, using methyl acrylic ester as function list
Body, ethylene glycol dimethacrylate are crosslinking agent, molar ratio 1:4~1:6；Addition accounts for function monomer and crosslinking agent is overall
The liquid metal microballoon of product 30%~60%, and be added and account for the photoinitiator 1800 of function monomer quality 1%~3% and prepare poly- third
Olefin(e) acid esters capillary monolithic column.Nitrogen is first passed through before polymerisation into mixed solution 15 minutes, to remove pre-polymer solution
In dissolved oxygen；Mixed solution is injected after capillary again and places 12h in 60 DEG C of hot bath, free radical in situ polymerization occurs
Reaction.
The methyl acrylic ester is that function monomer is 2- methacrylic acids, butyl methacrylate, metering system
Sour isobutyl ester and/or hydroxyethyl methacrylate.
The preparation method of the liquid metal microballoon is as follows：By liquid metal and surfactant in dispersed phase isopropanol
According to mass ratio 1:0.2：1 amount mixing, is ultrasonically treated, obtains dispersed liquid state molten drop later, will prepare the dispersion of gained
Liquid metal droplet carries out ultracentrifugation (25000rpm), after centrifuging 15 minutes, extracts removal supernatant, retains bottom deposit
Object adds isopropanol, centrifuges under these conditions, removes supernatant, which is repeated 3 times, to remove extra table
Face activating agent, then (- 40 DEG C) freeze-dryings of low temperature obtain liquid metal microsphere powder, are placed on spare in low temperature refrigerator；Institute
It states surfactant and is wrapped in liquid metal droplets surface, liquid metal surface tension can be made to be remarkably decreased, and the gold to be formed can be made
Surface orientation aligned transfer of the category drop in solution.It is total to by four amount of surfactant, temperature, ultrasonic power and time factors
With control liquid metal droplet diameter.
The surfactant is Tween 80, Span 80, that bent logical 100, cetyl trimethylammonium bromide and/or 12
Sodium alkyl sulfate.
Temperature is 15~50 DEG C when the supersound process；The ultrasonic power is 50~200W.
A diameter of 250nm~1200nm of the liquid metal microballoon.
The preparation method of the integral post further includes removal liquid metal microballoon as follows, specifically includes the integral post that will be obtained
Taking-up is connected on high pressure pump, controlled at 30 DEG C, first uses the conductive aqueous solution of saline media with 0.2mL/min flow velocitys
Integral post 6h is rinsed, to remove liquid metal microballoon；Again with methanol is rinsed, and to remove unreacted monomer in integral post, is obtained
The capillary monolithic column of controllable bore diameter and porosity.
The invention discloses a kind of simple and effectives using surfactant as the controllable diameter of molten drop surface coating layer
Droplet method, and be applied to normal as green pore-foaming agent replacement in the high-molecular porous integral post polymerization of adsorbing separation analysis
Advise the organic solvent of toxic high pollution.Simultaneously again by the effect of high-pressure water heating by liquid after high molecular polymer polymerize
Metal pore-foaming agent recycles after developing, to obtain possessing and adsorbing separation subject molecule in high-molecular porous material
The absorption hole and diffusion admittance that size matches.The adsorbing separation for reaching green, controllable bore diameter and porosity is high-molecular porous
Material preparation method.
A kind of sub-micron liquid metal microballoon of the present invention is the method that pore-foaming agent prepares integral post, with nanometer and micro-
The liquid metal droplet of rice diameter passes through liquid metal microspherulite diameter instead of the organic solvent pore-foaming agent of conventional toxic high pollution
Control realize control to integral post aperture.Prepare gained whole rod structure is uniform, permeability is good.The present invention solves
Processing after the size controlling of liquid metal ball and its preparation preserves, and is the technical barrier not solved in the prior art.
Description of the drawings
Fig. 1 present invention is with liquid metal microballoon transmission scanning electron microscope figure made from embodiment 1.
Fig. 2 present invention is with integral post scanning electron microscope (SEM) photograph made from embodiment 1.
The chromatography of 1 each compound of Fig. 3 embodiment of the present invention retains figure.
Specific implementation mode
It elaborates to the present invention with reference to embodiment.
Embodiment 1
Using liquid metal gallium as pore-foaming agent, the Tween 80 of the gallium of 0.5g and 0.1g is added in the isopropanol of 5mL, is controlled
Temperature is 20 DEG C, ultrasonic power 150W, ultrasound 30 minutes, and the dispersion liquid that particle size range is 250nm~1200nm is prepared
State molten drop.
The dispersed liquid state molten drop for preparing gained is subjected to ultracentrifugation (25000rpm), after centrifuging 15 minutes, is taken out
It removes and removes supernatant, retain basic sediment.10mL isopropanols are added, centrifuges under these conditions, remove supernatant, the behaviour
It is repeated 3 times, to remove extra surfactant.Frozen drying (- 40 DEG C) obtains liquid metal microballoon again
Powder.It places it in low temperature refrigerator (- 10 DEG C) and saves backup.
Using methacrylic acid as function monomer, ethylene glycol dimethacrylate is crosslinking agent, molar ratio 1:4.Add
Enter to account for the liquid metal microballoon of function monomer and crosslinking agent total volume 50%, and is added and accounts for function monomer and crosslinking agent gross mass
2% photoinitiator 1800 prepares integral post.Nitrogen is first passed through before polymerisation into mixed solution 15 minutes, to remove pre-polymerization
Close the dissolved oxygen in solution；It will polymerize 20min under ultraviolet light after mixed solution injection capillary again and obtain integral post.
The integral post both ends being prepared all are connected into PEEK tee connectors, it is defeated to be connected to high pressure by wherein one end PEEK
On liquid pump, other end PEEK is connected to sewer pipe.A port in the PEEK threeways of both ends is respectively inserted into platinum electrode, connects straight
Galvanic electricity source controls voltage 60V, electric current 0.03mA.It controls simultaneously and rinses mobile phase and whole column temperature at 30 DEG C, be first situated between with saliferous
The conductive aqueous solution of matter rinses integral post 6h with 0.2mL/min flow velocitys, to remove liquid metal microballoon.Then straight after deactivated power supply
It connects and 6h is rinsed with 0.2mL/min with methanol, to remove unreacted monomer in integral post to get to controllable bore diameter and porosity
Capillary monolithic column.One end of capillary monolithic column is connected to high-pressure pump with the PEEK casings of 2cm long and PEEK nuts.It is walked in enrichment
Suddenly, the flow that high-pressure pump is arranged is 0.12mL min-1, the sample solution of 5mL is made (to contain tetracycline, terramycin, fortimicin and gold
Each 20.0 μ g L of mycin-1) flow through capillary column；After enrichment, the flow for controlling high-pressure pump is 0.03mL min-1, make
The methanol of 0.1mL flows through capillary column, collects meoh eluate, for use HPLC/UV analyses.
Liquid phase chromatogram condition
Agilent 1260LC chromatographic systems.C18 columns (5 μm, 250mm × 4.6mm i.d.).Mobile phase：For acetonitrile (A)
With water (B), isocratic elution (A:B=35:65).Flow is 1.0mL min-1, 10 μ L, UV wavelength 355nm of sample size.
Those skilled in the art can be accurate according to other technological parameters described in explanation under the guidance of the present embodiment
Therefore in order to save examination resource, other embodiment is not listed in errorless reproduction the technical program.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (9)
1. application of the liquid metal microballoon as pore-foaming agent in preparing integral post.
2. application according to claim 1, which is characterized in that the liquid metal is gallium or gallium-indium liquid alloy.
3. application according to claim 1 or 2, which is characterized in that the preparation method of the integral post is as follows：Preparation solution
State metallic microspheres, using methyl acrylic ester as function monomer, ethylene glycol dimethacrylate is crosslinking agent, and molar ratio is
1:4~1:6；The liquid metal microballoon for accounting for function monomer and crosslinking agent total volume 30%~60% is added, and is added and accounts for function list
The photoinitiator of weight 1%~3% prepares polyacrylate capillary monolithic column.
4. application according to claim 3, which is characterized in that the methyl acrylic ester is that function monomer is 2- first
Base acrylic acid, butyl methacrylate, Isobutyl methacrylate and/or hydroxyethyl methacrylate.
5. application according to claim 3, which is characterized in that the preparation method of the liquid metal microballoon is as follows：By liquid
State metal is with surfactant according to mass ratio 1 in dispersed phase isopropanol:0.2:1 amount mixing, is ultrasonically treated, obtains later
The dispersed liquid state molten drop for preparing gained is carried out ultracentrifugation, after centrifuging 15 minutes, extracted by dispersed liquid state molten drop
Supernatant is removed, retains basic sediment, adds isopropanol, centrifuges under these conditions, remove supernatant, the operation is repeatedly
It carries out 3 times, to remove extra surfactant, then frozen drying obtains liquid metal microsphere powder；The surface
Activating agent is wrapped in liquid metal droplets surface, liquid metal surface tension can be made to be remarkably decreased, and can make the molten drop to be formed
In the surface orientation aligned transfer of solution.
6. application according to claim 5, which is characterized in that the surfactant is Tween 80, Span 80, Qu Natong
100, cetyl trimethylammonium bromide and/or lauryl sodium sulfate.
7. application according to claim 5, which is characterized in that temperature is 15~50 DEG C when the supersound process；It is described super
Acoustical power is 50~200W.
8. application according to claim 3, which is characterized in that a diameter of 250nm of the liquid metal microballoon~
1200nm。
9. application according to claim 3, which is characterized in that the preparation method of the integral post further includes removal liquid as follows
State metallic microspheres specifically include the integral post both ends that will be made and all connect PEEK tee connectors, and wherein one end PEEK connects
It is connected on high pressure pump, other end PEEK is connected to sewer pipe；A port in the PEEK threeways of both ends is respectively inserted into platinum filament
Electrode connects DC power supply, controls voltage 30V~120V, electric current 0.01mA~0.5mA；It controls simultaneously and rinses mobile phase and whole
Scapus temperature first uses the conductive aqueous solution of saline media to rinse integral post between 25 DEG C~35 DEG C, micro- to remove liquid metal
Ball；It is directly rinsed with methanol after deactivating power supply, to remove unreacted monomer in integral post, obtains controllable bore diameter and porosity
Organic polymer solid chromatography column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810240781.XA CN108421542B (en) | 2018-03-22 | 2018-03-22 | Application of liquid metal microspheres as pore-forming agent in preparation of monolithic column |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810240781.XA CN108421542B (en) | 2018-03-22 | 2018-03-22 | Application of liquid metal microspheres as pore-forming agent in preparation of monolithic column |
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| Publication Number | Publication Date |
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| CN108421542A true CN108421542A (en) | 2018-08-21 |
| CN108421542B CN108421542B (en) | 2020-08-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111763276A (en) * | 2019-04-02 | 2020-10-13 | 中国科学院青岛生物能源与过程研究所 | Liquid metal/high polymer composite dielectric material and preparation method thereof |
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| CN103068939A (en) * | 2010-08-26 | 2013-04-24 | 原子能和替代能源委员会 | Liquid metal emulsion |
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Patent Citations (6)
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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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| CN111763276A (en) * | 2019-04-02 | 2020-10-13 | 中国科学院青岛生物能源与过程研究所 | Liquid metal/high polymer composite dielectric material and preparation method thereof |
| CN111763276B (en) * | 2019-04-02 | 2022-04-29 | 中国科学院青岛生物能源与过程研究所 | Liquid metal/high polymer composite dielectric material and preparation method thereof |
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| CN108421542B (en) | 2020-08-07 |
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