CN103861555A - Preparation method of multi-porous silica gel liquid chromatographic monolithic column - Google Patents
Preparation method of multi-porous silica gel liquid chromatographic monolithic column Download PDFInfo
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- CN103861555A CN103861555A CN201310669178.0A CN201310669178A CN103861555A CN 103861555 A CN103861555 A CN 103861555A CN 201310669178 A CN201310669178 A CN 201310669178A CN 103861555 A CN103861555 A CN 103861555A
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Abstract
The invention discloses a preparation method of a multi-porous silica gel liquid chromatographic monolithic column. The monolithic column is obtained by performing crosslinking reaction on polymethylhydrosiloxane (PHMS) and 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane (D4Vi) which serve as precursors and poly styrene (PS) microspheres which are prepared by a dispersion and polymerization method and serve as a template; the monolithic column has a microporous and macroporous double-hole structure; the porosity is over 80 percent; the hole diameter is ranged from 20 nanometers to 2.6 microns; the hole volume is 7cm<3>/g; the specific surface area is 210m<2>/g. The preparation method disclosed by the invention is simple in technology, precise and short in period; the formation of the multi-porous structure is controllable; the obtained silica gel monolithic column is stable in chromatographic performance, high in repetitiveness, high in mechanical stability and high in column efficiency. A catalyst is particularly suitable for low-pressure, quick and high-efficiency separation of high performance liquid chromatography.
Description
Technical field
The invention relates to chromatographic separation technology, more particularly, relate to a kind of preparation method of silica matrix integral post.
Background technology
In recent years, the application of high performance liquid chromatography (HPLC) in compartment analysis is more and more extensive, and in piece-rate system, chromatographic column is again the core of chromatographic technique.But mostly what sold market at present is particles filled type chromatographic column, and packing material size is less, and separating effect is better, the increase that simultaneously causes post to press is more harsh to the requirement of equipment performance and operating technology.And integral post can effectively address these problems.Integral post adopts in-situ synthetic method more, has macropore, micropore double-pore structure, good mechanical stability, and post effect is high, can meet low pressure, requirement efficient, that separate fast, therefore becomes the target that vast chromatogram worker competitively studies.At present, monolithic silica column is a kind of main integral post type, but the preparation of monolithic silica column adopts sol-gal process more, and cycle length, distortion easy to crack, poor repeatability become the bottleneck of its development.
Summary of the invention
Object of the present invention, be to overcome the shortcoming and defect of existing HPLC monolithic silica column manufacturing cycle length, distortion easy to crack, poor repeatability, a kind of excellent separating property that has is provided, be applicable to being applied in high performance liquid chromatography the preparation method of the simple liquid chromatogram Bio-sil of preparation process integral post.
Object of the present invention is achieved by following technical proposals.
A preparation method for liquid chromatogram Bio-sil integral post, has following steps:
(1) utilize dispersion copolymerization method to prepare polystyrene and be called for short PS microsphere template
Be 60:7 composition mixed solvent according to the mass fraction of distilled water and absolute ethyl alcohol, polyvinylpyrrolidone be called for short to PVP and be dissolved in this mixed solvent, the mass fraction of PVP and above-mentioned mixed solvent is 2:67; Above-mentioned mixed system is dropped into and is equipped with in the four-hole bottle of 250ml of thermometer, agitator and condenser, pre-dispersed 30min under nitrogen protection effect, on this basis, adding mass fraction is that to be called for short St and mass fraction be that the initator azodiisobutyronitrile of 0.3 part is called for short AIBN for the monomer styrene of 30 parts again, constant temperature water bath reacts 12h at 70 DEG C, again reacted solution is carried out to suction filtration, dry, grinding, obtain white powder polystyrene microsphere;
(2) prepare pre-column
Take polystyrene microsphere prepared by step (1) and be dissolved in mass fraction in the ethanol of 3 parts taking mass fraction as 2～4 parts, ultrasonic dispersion 15min dissolves completely to polystyrene microsphere, then the hydrogen containing siloxane that is 5 parts by mass fraction to be called for short PHMS and mass fraction be the tetrem thiazolinyl tetramethyl-ring tetrasiloxane abbreviation D of 5 parts
4the mixed solution of Vi joins in beaker, continues ultrasonic dispersion 30min and forms dispersed system; In beaker, drip again mass fraction and be the ethylene methacrylic radical siloxane coordination platinum catalyst of 0.1 part, control water temperature ultrasonic dispersion 1h at 30 DEG C; Above-mentioned precursor solution is utilized vavuum pump to vacuumize to process and remove residual solvent, then be injected in glass tube mould and be placed in baking oven in 50 DEG C of insulation 4h, then be warming up to 80 DEG C of insulation 5h, obtain prefabricated post;
(3) high temperature burning-off polystyrene moulding
The prefabricated post of step (2) is placed in to Muffle furnace, is warming up to 750 DEG C with the speed of 3 DEG C/min from room temperature, constant temperature 60min heat-treats to remove template, obtains having the liquid chromatogram Bio-sil integral post of through-hole structure.
The glass tube mould of described step (2) is 50mm × 4.6mm i.d..
Described Bio-sil integral post has the double-pore structure of micropore and macropore, and porosity is greater than 80%, and pore-size distribution concentrates on 20nm and 2.6 μ m, and pore volume is 7cm
3/ g, specific area reaches 210m
2/ g.
The present invention compared with prior art, advantage is that preparation cost is low, preparation method is simple, accurate, the cycle is short, the formation of loose structure is controlled, prepared Bio-sil integral post chromatographic performance is stable, separating effect with reproducible, mechanical stability strong, post effect is high, be specially adapted to the low pressure of high performance liquid chromatography, fast, efficiently separation.The present invention has micropore and macropore double-pore structure, and porosity is greater than 80%, and pore-size distribution concentrates on 20nm and 2.6 μ m, and pore volume is 7cm
3/ g, specific area is up to 210m
2/ g.
Brief description of the drawings
Fig. 1 is the SEM figure of embodiment 1 liquid chromatogram Bio-sil integral post;
Fig. 2 is embodiment 1 liquid chromatogram Bio-sil integral post adsorption/desorption isotherms;
Fig. 3 is embodiment 1 liquid chromatogram Bio-sil integral post graph of pore diameter distribution;
Fig. 4 is the SEM figure that utilizes the synthetic PS template microsphere of dispersion copolymerization method;
Fig. 5 is the liquid chromatogram Bio-sil integral post SEM figure of embodiment 2;
Fig. 6 is the liquid chromatogram Bio-sil integral post SEM figure of embodiment 1;
Fig. 7 is the liquid chromatogram Bio-sil integral post SEM figure of embodiment 3;
Fig. 8 is the liquid chromatogram Bio-sil integral post SEM figure of embodiment 4;
Fig. 9 is that embodiment 1 liquid chromatogram Bio-sil integral post is as the fixing separating resulting with respect to acetone of liquid-phase chromatographic column;
Figure 10 is that embodiment 1 liquid chromatogram Bio-sil integral post is as the fixing separating resulting with respect to benzene of liquid-phase chromatographic column.
Detailed description of the invention
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
The present invention is raw materials used: ethanol (C
2h
5oH,>=99.7%) purchased from Li Anlongbohua (Tianjin) medical chemistry Co., Ltd; Monomer styrene (St,>=98.0%) is purchased from Tianjin chemical reagent one factory; Polyvinylpyrrolidone (analyzing pure) is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Azodiisobutyronitrile (AIBN analyzes pure) is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Hydrogen containing siloxane (PHMS, hydrogen content: 1.6wt.%, density p: 1g/cm
3) purchased from Zhejiang three Tai Youjiguicailiaochang; Tetramethyl tetrem thiazolinyl cyclotetrasiloxane (D
4vi, density p: 1g/cm
3) purchased from Zhejiang San Men thousand rainbow Industrial Co., Ltd.s; Ethylene methacrylic radical siloxane coordination platinum catalyst (platinum content: 300ppm) is purchased from Shenzhen platinum complex Co., Ltd.
2.0gPVP is dissolved in the mixed solvent of 60.4g ethanol and 7.6g water composition; and its input is equipped with in the four-hole bottle of 250ml of thermometer, agitator and condenser; pre-dispersed 30min under nitrogen protection effect; add afterwards 30.0g monomer St and 0.3g initiator A IBN; constant temperature water bath reacts 12h at 70 DEG C, and reacted solution is carried out to suction filtration, and filter cake is dried; grind, obtain the sample of the PS microballoon of white powder.
Weigh 3g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic dispersion 15min dissolves completely to polystyrene, afterwards respectively by 5gPHMS and 5gD
4the mixed solution of Vi joins in beaker, continue ultrasonic dispersion 30min and form dispersed system, in beaker, drip again 0.1g coordination platinum catalyst control water temperature ultrasonic dispersion 1h at 30 DEG C, above-mentioned soln using water pump is carried out to application of vacuum to it and remove residual solvent, and be injected in glass tube, to be put in baking oven heat 4h at 50 DEG C, after be warming up to 80 DEG C of heating 5h and obtain prefabricated post.
Prefabricated post, in Muffle furnace, is warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treats and remove template, obtain having the liquid chromatogram Bio-sil integral post of through-hole structure.
In the present embodiment, the preparation process of polystyrene microsphere is with embodiment mono-.Different: weigh 2g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic dispersion 15min dissolves completely to polystyrene, afterwards respectively by 5gPHMS and 5gD
4the mixed solution of Vi joins in beaker, continue ultrasonic dispersion 30min and form dispersed system, in beaker, drip again 0.1g coordination platinum catalyst control water temperature ultrasonic dispersion 1h at 30 DEG C, above-mentioned soln using water pump carries out application of vacuum to it and removes residual solvent, and be injected in glass tube, to be put in baking oven heat 4h at 50 DEG C, after be warming up to 80 DEG C of heating 5h and obtain prefabricated post.
Prefabricated post, in Muffle furnace, is warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treats and remove template, obtain having the liquid chromatogram Bio-sil integral post of through-hole structure.
Embodiment 3
In the present embodiment, the preparation process of polystyrene microsphere is with embodiment mono-.Different: weigh 3.5g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic dispersion 15min dissolves completely to polystyrene, afterwards respectively by 5gPHMS and 5gD
4the mixed solution of Vi joins in beaker, continue ultrasonic dispersion 30min and form dispersed system, in beaker, drip again 0.1g coordination platinum catalyst control water temperature ultrasonic dispersion 1h at 30 DEG C, above-mentioned soln using water pump carries out application of vacuum to it and removes residual solvent, and be injected in glass tube, to be put in baking oven heat 4h at 50 DEG C, after be warming up to 80 DEG C of heating 5h and obtain prefabricated post.
Prefabricated post, in Muffle furnace, is warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treats and remove template, obtain having the liquid chromatogram Bio-sil integral post of through-hole structure.
Embodiment 4
In the present embodiment, the preparation process of polystyrene microsphere is with embodiment mono-.Different: weigh 4g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic dispersion 15min dissolves completely to polystyrene, afterwards respectively by 5gPHMS and 5gD
4the mixed solution of Vi joins in beaker, continue ultrasonic dispersion 30min and form dispersed system, in beaker, drip again 0.1g coordination platinum catalyst control water temperature ultrasonic dispersion 1h at 30 DEG C, above-mentioned soln using water pump carries out application of vacuum to it and removes residual solvent, and be injected in glass tube, to be put in baking oven heat 4h at 50 DEG C, after be warming up to 80 DEG C of heating 5h and obtain prefabricated post.
Prefabricated post, in Muffle furnace, is warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treats and remove template, obtain having the liquid chromatogram Bio-sil integral post of through-hole structure.
As can see from Figure 1, the integral post pre-column of preparing as template taking the synthetic PS microballoon of dispersion copolymerization method has retained the loose structure skeleton of PS microballoon after pyrolysis, the phenomenon of caving in.Meanwhile, the overall distribution in hole is comparatively orderly, evenly, is communicated with.Pore diameter range concentrates on 20nm and 2.6 μ m, and macropore is even, dispersion, nested against one another with aperture.After above-mentioned analysis shows to utilize PS microballoon for template carbonization, its microscopic appearance has obtained high-precision copying, and prepares the liquid chromatogram monolithic silica column of ordered porous structural.
As can be seen from Figure 2, the branch of Liang Ge up and down of N adsorption/desorption curve is comparatively close, is H1 type thermoisopleth.Illustrate that liquid chromatogram monolithic silica column prepared by the present invention has through-hole structure, pass is more even, regular, similar spheroidal.
From Fig. 3, the graph of pore diameter distribution of monolithic silica column can be found out, pore diameter range concentrates on 20nm and 2.6 μ m, has very large specific area 210m simultaneously
2/ g, (adopting U.S. Quanta Chrome NOVA-2000 type ratio surface area instrument to carry out the mensuration of specific area) has macropore and microcellular structure simultaneously, and its pore volume is higher than packed column, and porosity is greater than 80%.
As can be seen from Figure 4, the PS microballoon that dispersion copolymerization method is synthetic, its particle diameter is 2.6 μ m, uniform particle diameter, favorable dispersibility.
Be PS2 part mass fraction from Fig. 5～8(Fig. 5, Fig. 6 is PS3 part mass fraction, and Fig. 7 is PS3.5 part mass fraction, and Fig. 8 is PS4 part mass fraction) analyze the impact of PS microsphere template content on integral post.Can find out, along with the increase of PS microballoon consumption, hole number increases, and porosity also significantly improves.When PS microballoon content is 3 parts of mass fractions, on cross section, the quantity of pore structure is maximum, forms connected pore channel, the region minimum that matrix material is shared, and pore structure proportion is maximum and evenly, skeleton has certain hardness; When PS microballoon content is higher than 3 parts of mass fractions, the quantity in hole does not increase thereupon, but reduces to some extent, and meanwhile, the phenomenon of caving in is fairly obvious, the out-of-flatness of matrix material cross section, and skeleton is discontinuous; Along with PS microballoon amount increases, in cross-linking process, participate in the template number of " pore-creating " too much on the other hand, in dispersion process, may disperse inhomogeneously, reunite, thereby cause aperture excessive.
From scanning electron microscope (SEM) photograph, also confirmed this point, therefore this integral post has higher apparent porosity.In the time that PS content is 3 parts of mass fractions, PS content reaches amounts of optimization.
Finally, on liquid chromatograph (Shimadzu LC-10AD), carry out separating substances after packing product of the present invention into chromatographic column, check its separating effect as the fixing phase of liquid-phase chromatographic column.
As can be seen from Figure 9: separated material is that (molecular weight is 58.08 to acetone, purchased from sky over the river Chemical Engineering Technology Co., Ltd), adopt RP chromatography, mobile phase is that (molecular weight is 32.04 to methyl alcohol, analyze pure, purchased from Tianjin Chemical Reagents Factory No.1), ultraviolet detect wavelength be 254nm, flow velocity is 1mL/min, and post is pressed as 6kg/cm
2, the dead time is shorter, and separating effect is better.According to theoretical cam curve computing formula N==5.54 (Tr/W
1/2)
2(retention time that wherein Tr is tested component, W
1/2for half-peak breadth, i.e. the half of top peak width.) the post effect calculated is 6000N/m.
As can be seen from Figure 10: separated material is that (molecular weight is 78.11 to benzene, purchased from Tianjin chemical reagent two factories), adopt forward chromatography, mobile phase is that (molecular weight is 84.16 to cyclohexane, analyze pure, purchased from Tianjin Chemical Reagents Factory No.1), ultraviolet detect wavelength be 254nm, flow velocity is 1mL/min, and post is pressed as 10kg/cm
2, separating effect is better and peak shape is sharp-pointed, according to theoretical cam curve computing formula N==5.54 (Tr/W
1/2)
2(retention time that wherein Tr is tested component, W
1/2for half-peak breadth, i.e. the half of top peak width.) the post effect calculated is 11080N/m.
Fig. 9 and Figure 10 have proved that result of the present invention, have good application aspect the fixing phase of liquid-phase chromatographic column, also can reach good separating effect under the condition particularly separating in low pressure.
Claims (3)
1. a preparation method for liquid chromatogram Bio-sil integral post, has following steps:
(1) utilize dispersion copolymerization method to prepare polystyrene and be called for short PS microsphere template
Be 60:7 composition mixed solvent according to the mass fraction of distilled water and absolute ethyl alcohol, polyvinylpyrrolidone be called for short to PVP and be dissolved in this mixed solvent, the mass fraction of PVP and above-mentioned mixed solvent is 2:67; Above-mentioned mixed system is dropped into and is equipped with in the four-hole bottle of 250ml of thermometer, agitator and condenser, pre-dispersed 30min under nitrogen protection effect, on this basis, adding mass fraction is that to be called for short St and mass fraction be that the initator azodiisobutyronitrile of 0.3 part is called for short AIBN for the monomer styrene of 30 parts again, constant temperature water bath reacts 12h at 70 DEG C, again reacted solution is carried out to suction filtration, dry, grinding, obtain white powder polystyrene microsphere;
(2) prepare pre-column
Take polystyrene microsphere prepared by step (1) and be dissolved in mass fraction in the ethanol of 3 parts taking mass fraction as 2～4 parts, ultrasonic dispersion 15min dissolves completely to polystyrene microsphere, then the hydrogen containing siloxane that is 5 parts by mass fraction to be called for short PHMS and mass fraction be the tetrem thiazolinyl tetramethyl-ring tetrasiloxane abbreviation D of 5 parts
4the mixed solution of Vi joins in beaker, continues ultrasonic dispersion 30min and forms dispersed system; In beaker, drip again mass fraction and be the ethylene methacrylic radical siloxane coordination platinum catalyst of 0.1 part, control water temperature ultrasonic dispersion 1h at 30 DEG C; Above-mentioned precursor solution is utilized vavuum pump to vacuumize to process and remove residual solvent, then be injected in glass tube mould and be placed in baking oven in 50 DEG C of insulation 4h, then be warming up to 80 DEG C of insulation 5h, obtain prefabricated post;
(3) high temperature burning-off polystyrene moulding
The prefabricated post of step (2) is placed in to Muffle furnace, is warming up to 750 DEG C with the speed of 3 DEG C/min from room temperature, constant temperature 60min heat-treats to remove template, obtains having the liquid chromatogram Bio-sil integral post of through-hole structure.
2. according to the preparation method of a kind of liquid chromatogram Bio-sil integral post of claim 1, it is characterized in that, the glass tube mould of described step (2) is 50mm × 4.6mm i.d..
3. according to the preparation method of a kind of liquid chromatogram Bio-sil integral post of claim 1, it is characterized in that, described Bio-sil integral post has the double-pore structure of micropore and macropore, and porosity is greater than 80%, pore-size distribution concentrates on 20nm and 2.6 μ m, and pore volume is 7cm
3/ g, specific area reaches 210m
2/ g.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502420A (en) * | 2016-01-25 | 2016-04-20 | 天津大学 | Fully-hollow silicon dioxide microsphere stationary phase and preparation method thereof |
| WO2016178560A1 (en) | 2015-05-06 | 2016-11-10 | Separex S.A.S. | Hydrophobic silica aerogel and method for the preparation thereof |
| CN108786764A (en) * | 2018-05-07 | 2018-11-13 | 安徽师范大学 | Thiophilic integral material of organic-silica gel hybridization and its preparation method and application |
| CN111801151A (en) * | 2018-11-07 | 2020-10-20 | 川崎重工业株式会社 | Acid gas absorbing material and method for producing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101975835A (en) * | 2010-10-13 | 2011-02-16 | 天津大学 | Ordered pore-structured silica gel monolithic column and preparation method thereof |
| CN102728329A (en) * | 2012-06-14 | 2012-10-17 | 天津大学 | Porous silica gel used as liquid chromatography stationary phase material and preparation method thereof |
| CN103406112A (en) * | 2013-07-29 | 2013-11-27 | 天津大学 | Silica gel monolithic column for HPLC and preparation method thereof |
-
2013
- 2013-12-10 CN CN201310669178.0A patent/CN103861555A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101975835A (en) * | 2010-10-13 | 2011-02-16 | 天津大学 | Ordered pore-structured silica gel monolithic column and preparation method thereof |
| CN102728329A (en) * | 2012-06-14 | 2012-10-17 | 天津大学 | Porous silica gel used as liquid chromatography stationary phase material and preparation method thereof |
| CN103406112A (en) * | 2013-07-29 | 2013-11-27 | 天津大学 | Silica gel monolithic column for HPLC and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016178560A1 (en) | 2015-05-06 | 2016-11-10 | Separex S.A.S. | Hydrophobic silica aerogel and method for the preparation thereof |
| CN105502420A (en) * | 2016-01-25 | 2016-04-20 | 天津大学 | Fully-hollow silicon dioxide microsphere stationary phase and preparation method thereof |
| CN108786764A (en) * | 2018-05-07 | 2018-11-13 | 安徽师范大学 | Thiophilic integral material of organic-silica gel hybridization and its preparation method and application |
| CN108786764B (en) * | 2018-05-07 | 2021-09-28 | 安徽师范大学 | Organic-silica gel hybrid thiophilic monolithic material and preparation method and application thereof |
| CN111801151A (en) * | 2018-11-07 | 2020-10-20 | 川崎重工业株式会社 | Acid gas absorbing material and method for producing same |
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Application publication date: 20140618 |