CN103406112B - Silica gel monolithic column for HPLC and preparation method thereof - Google Patents
Silica gel monolithic column for HPLC and preparation method thereof Download PDFInfo
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- CN103406112B CN103406112B CN201310322930.4A CN201310322930A CN103406112B CN 103406112 B CN103406112 B CN 103406112B CN 201310322930 A CN201310322930 A CN 201310322930A CN 103406112 B CN103406112 B CN 103406112B
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Abstract
The invention discloses a silica gel monolithic column for HPLC (High Performance Liquid Chromatography) and a preparation method thereof. Firstly, polystyrene template small balls are prepared through the emulsion polymerization method, then, the polystyrene template is dissolved in reactants of linear hydrogen-containing polysiloxane and annular tetravinyl tetramethyl cyclotetrasiloxane for crosslinking reaction to obtain a prefabricated column; finally, the polystyrene template is burned at high temperature; the monolithic column with through holes are obtained after heat treatment. According to the invention, the problem of a conventional particle packed column for HPLC is overcome, and the silica gel monolithic column for HPLC and the preparation method thereof are provided; the monolithic column has excellent separation performance, and is suitable for HPLC, and the preparation method is simple.
Description
Technical field
The invention belongs to high-efficiency liquid phase chromatography integral post technology, more particularly, relate to a kind of silica matrix integral post and preparation method thereof.
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 market was sold at present is particles filled type chromatographic column, and packing material size is less, and separating effect is better, cost also can be higher simultaneously.Therefore, the target that synthesis preparation is simple, cost integral post that is low, good separating effect becomes vast chromatogram worker pursuit.At present, organic silica gel integral post is a kind of main integral post type.Compared with traditional particles filled post, integral post have low pressure, fast, the advantage such as efficient, mechanical strength is high and column performance is stable, in separation field, play more and more important effect.Present stage, commercial particulate packed column mostly was the filler of 5-10 μm, also existed that porosity is little, back pressure large, hold susceptible to plugging shortcoming.In addition, in separation process, relate to that particle easily comes off under the washing away of mobile phase, the problem such as to cave in.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, overcome the problem of the particles filled post of existing HPLC, performance liquid chromatographic column is made integral post, fabricated in situ monolithic silica column in void column, this integral post has excellent separating property, be applicable to being applied in high performance liquid chromatography, its preparation method process is simple.
Technical purpose of the present invention is achieved by following technical proposals:
Silica gel monolithic column for HPLC and preparation method thereof, utilizes polystyrene microsphere as template, by linear hydrogen containing siloxane (PHMS) and t etram-ethyltetravinylcyclotetrasiloxane (D
4vi) carry out in-situ cross-linkedly obtaining prefabricated post (being namely cross-linked in tubing string), the polystyrene microsphere in recycling high temperature removing prefabricated post, can obtain the chromatography silica gel integral post with through-hole structure.Specifically,
Described polystyrene microsphere selects the polystyrene microsphere often selected in method for preparing template, polystyrene (PS) microballoon is prepared as utilized emulsion polymerization, but need the even particle size distribution of the polystyrene microsphere selected, comparatively single, the such as PS microballoon of emulsion polymerization synthesis, its particle diameter is 200nm, and favorable dispersibility.Use the mixed solvent (decentralized medium) of distilled water and absolute ethyl alcohol composition; wherein ethanol mass fraction is 30 parts; the mass fraction of distilled water is 100 parts; the pH=9 (or pH>7) of decentralized medium is regulated by pH value regulator; drip the ethanol solution of butyl titanate; temperature is increased to 75 DEG C; add emulsifying agent dodecyl sodium sulfate; styrene is dripped under nitrogen protection; and then add initiator ammonium persulfate; styrene is polymerized on the surface of titania gel, then at 75 DEG C, isothermal reaction 8h.The emulsion obtained is crossed and filters insoluble matter, breakdown of emulsion, filtration, washing, vacuum drying is carried out with the sodium hydrate aqueous solution of 5% (mass fraction), obtain the PS sample (Tang Rongnian of white powder, the photonic crystal of opals structure preparation and characterization of PS/TiO2 composite, electronic component and material, 2003).
In technical solution of the present invention, select to carry out in tubing string in-situ cross-linked to prepare prefabricated post, carry out according to following step:
Take 0.5-2 mass fraction polystyrene microspheres in ethanol dispersed, the hydrogen containing siloxane of mass fraction and the t etram-ethyltetravinylcyclotetrasiloxane such as then to add and be dispersed into homogeneous system, add coordination platinum catalyst wherein again, control temperature proceeds dispersion at being 20-30 DEG C, until after there is crosslinking phenomena (namely the phenomenon of the cross-linking reactions such as sticky and viscosity rising appears in system), be injected in mould and can obtain prefabricated post at 50-80 DEG C of heating 4-12h.
In above-mentioned preparation process, ultrasonic disperse mode is selected to disperse system.
In above-mentioned preparation process, described coordination platinum catalyst selects methyl vinyl silicone coordination platinum catalyst (platinum content: 300ppm) purchased from Shenzhen platinum complex Co., Ltd, and its chemical formula is as follows:
Catalyst charge is 1%-3% of hydrogen containing siloxane and t etram-ethyltetravinylcyclotetrasiloxane gross mass, the speed that the number major effect cross-linking reaction of its addition is carried out.
In above-mentioned preparation process, after there is crosslinking phenomena, after selecting pump to carry out the residual etoh solvent of application of vacuum removal to system, then carry out injection mould.
In above-mentioned preparation process, the needs that described mould uses according to reality are processed, with the requirement making the prefabricated post of preparation substantially meet shape size in actual use.
In above-mentioned preparation process, be injected into after in mould, preferably at 60-70 DEG C of heating 6-10h, to meet the needs completing crosslinked and abundant solvent flashing ethanol as far as possible.
After the preparation having carried out prefabricated post, prefabricated post is placed in Muffle furnace, is warming up to 750 DEG C of constant temperature 60min with the speed of 3 DEG C/min from room temperature 20-25 DEG C and heat-treats removing template, namely obtain the required integral post with through-hole structure.
Monolithic silica column prepared by the present invention, has through-hole structure, and pass is comparatively even, and pore diameter range concentrates on 30-35nm, has very large specific area 500-550m simultaneously
2/ g, (adopting U.S. QuantaChromeNOVA-2000 type ratio surface area instrument to carry out the mensuration of specific area), have macropore and central hole structure, its pore volume is higher than packed column, and porosity is greater than 80% simultaneously.This structure is close to the filler of through-flow chromatogram, even if use higher flow velocity, too large fluid resistance is not had yet, this integral post has high speed, low pressure, efficient, the feature that is suitable for gradient elution, is well suited for and carries out efficiently, being fast separated to the sample of the macromolecule as protein.The SEM that shows with reference to the accompanying drawings (by the sample for preparing after metal spraying process, utilizing the pattern of the sample under the XL30ESEM cold field emission sem observation different situations of Dutch Phlilps company) photo is known:
Can see that from accompanying drawing 1 the integral post pre-column being Template preparation with the PS bead of emulsion polymerization synthesis, although cause weightlessness owing to shrinking after pyrolysis, remains the loose structure skeleton of PS, do not have phenomenon of caving in.Meanwhile, the overall distribution in hole is comparatively orderly, and pore diameter range concentrates on 30-35nm.Above-mentioned analysis shows to utilize PS to obtain high-precision copying for its microscopic appearance after template carbonization, prepares the monolithic silica column of ordered porous structural.
As can be seen from accompanying drawing 2 and accompanying drawing 3, monolithic silica column prepared by the present invention, has through-hole structure, and pass is comparatively even, and pore diameter range concentrates on 30-35nm, has very large specific area 500-550m simultaneously
2/ g, (adopting U.S. QuantaChromeNOVA-2000 type ratio surface area instrument to carry out the mensuration of specific area), have macropore and central hole structure, its pore volume is higher than packed column, and porosity is greater than 80% simultaneously.
As can be seen from accompanying drawing 4, the PS microballoon of emulsion polymerization synthesis, its particle diameter is 200nm, favorable dispersibility.Analyze PS template content to the impact of integral post from accompanying drawing 5-9, as can be seen from the figure, along with the increase of PS consumption, also there is certain increase in corresponding aperture.Analyze known, although due to the contraction in pyrolytic process, the pore size obtained may be declined.But, along with the continuous increase of PS template addition, the template number participating in " pore-creating " in cross-linking process is increased, may occur reunite and cause aperture to become large in pyrolytic process.As can be seen from the figure along with the increase of PS consumption, porosity also significantly improves, this is because along with the increase of PS content, the template number of " pore-creating " is corresponding to be increased, a large amount of open pores is formed in heat treatment process, arrange comparatively orderly between hole and form connected pore channel, from scanning electron microscope (SEM) photograph, also demonstrate that this point, therefore this integrated injection has higher apparent porosity.When PS content is 2 parts of mass fractions, form connected pore channel, PS content reaches amounts of optimization.
Finally, on liquid chromatograph (Shimadzu LC-10AD), carry out separating substances after product of the present invention is loaded chromatographic column, check it as the separating effect of liquid-phase chromatographic column Stationary liquid.As can be seen from accompanying drawing 10: separated material is acetone (molecular weight is 58.08, purchased from sky over the river Chemical Engineering Technology Co., Ltd), adopt RP chromatography, mobile phase is redistilled water, and UV detect wavelength is 254nm, and flow velocity is 1mL/min, and post pressure is 50kg/cm
2, the dead time is shorter, and separating effect is better.As can be seen from accompanying drawing 11: separated material is that (molecular weight is 78.11 to benzene, purchased from Tianjin chemical reagent two factory), adopt forward chromatography, mobile phase is that (molecular weight is 84.16 to cyclohexane, analyze pure, purchased from Tianjin Chemical Reagents Factory No.1), UV detect wavelength is 254nm, flow velocity is 1mL/min, and post pressure is 40kg/cm
2, separating effect is better and peak shape symmetry is good, according to theoretical cam curve computing formula N==5.54 (Tr/W
1/2)
2the post effect calculated is 622.5, and wherein Tr is the retention time of tested component, W
1/2for half-peak breadth, i.e. the half of top peak width.Above two examples proves result of the present invention has good application as in liquid-phase chromatographic column Stationary liquid, also can reach good separating effect under the condition be particularly separated in low pressure.
Compared with prior art, the invention has the advantages that preparation cost is low, preparation method's process is simple; Made monolithic silica column has the high and good separating effect of certain mechanical strength, stability, and this integral post is specially adapted to the compartment analysis of high performance liquid chromatography.
Accompanying drawing explanation
Fig. 1 is the SEM photo of monolithic silica column.
Fig. 2 is monolithic silica column adsorption/desorption isotherms.
Fig. 3 is monolithic silica column graph of pore diameter distribution.
Fig. 4 is the SEM photo of the polystyrene moulding microballoon utilizing dispersion copolymerization method to synthesize.
Fig. 5 is the monolithic silica column SEM photo under the PS template content of embodiment 5.
Fig. 6 is the monolithic silica column SEM photo under the PS template content of embodiment 4.
Fig. 7 is the monolithic silica column SEM photo under the PS template content of embodiment 3.
Fig. 8 is the monolithic silica column SEM photo under the PS template content of embodiment 2.
Fig. 9 is the monolithic silica column SEM photo under the PS template content of embodiment 1.
Figure 10 be monolithic silica column as the separating resulting for acetone after liquid-phase chromatographic column Stationary liquid, wherein abscissa is retention time (min), and ordinate is intensity.
Figure 11 be monolithic silica column as the separating resulting for benzene after liquid-phase chromatographic column Stationary liquid, wherein abscissa is retention time (min), and ordinate is intensity.
Detailed description of the invention
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.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; Initator dodecyl sodium sulfate (analyzing pure) is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Ammonium persulfate (analyzing pure) is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Butyl titanate (>=99.8%) is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; NaOH (analyzing pure) is purchased from huge chemical experimental factory, Tianjin; Hydrogen containing siloxane (PHMS, hydrogen content: 1.6wt.%, density p: 1g/cm
3) purchased from Zhejiang three Tai Youjiguicailiaochang; T etram-ethyltetravinylcyclotetrasiloxane (D4Vi, density p: 1g/cm
3) purchased from Zhejiang San Men thousand rainbow Industrial Co., Ltd.; Methyl vinyl silicone coordination platinum catalyst (platinum content: 300ppm) is purchased from Shenzhen platinum complex Co., Ltd.
Embodiment 1
The distilled water of 100ml and the absolute ethyl alcohol of 30ml is added in the there-necked flask of 250ml, the pH=9 (or PH>7) of decentralized medium is regulated by pH value regulator, drip the ethanol solution of the butyl titanate of 10.0ml4% (mass fraction), stirring reaction 40min at 40 DEG C, obtains stable titania gel.Temperature is increased to 75 DEG C; add emulsifying agent dodecyl sodium sulfate 0.2g, under nitrogen protection, drip the styrene of 5.0ml, and then add the initiator ammonium persulfate of 0.2g; styrene is polymerized, then isothermal reaction 8h at 75 DEG C on the surface of titania gel.The emulsion obtained is crossed and filters insoluble matter, carry out breakdown of emulsion, filtration, washing, vacuum drying with the sodium hydroxide solution of 5% (mass fraction), obtain the sample of the PS microballoon of white powder.
Weighing 2g polystyrene microsphere is dissolved in 3g ethanol, ultrasonic disperse 15min dissolves completely to polystyrene, each mixed solution by 5gPHMS and 5gD4Vi joins in beaker afterwards, continue ultrasonic disperse 30min and form dispersed system, in beaker, drip 0.1g coordination platinum catalyst again control water temperature ultrasonic disperse 1h at 30 DEG C, there will be obvious crosslinking phenomena.Utilize water pump to carry out application of vacuum to it to above-mentioned solution 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.
By prefabricated post in Muffle furnace, be warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treat removing template, namely obtain the required integral post with through-hole structure.
Embodiment 2
In the present embodiment, the preparation process of polystyrene microsphere is with embodiment one.Unlike: weigh 1.5g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic disperse 15min dissolves completely to polystyrene, each mixed solution by 5gPHMS and 5gD4Vi joins in beaker afterwards, continue ultrasonic disperse 30min and form dispersed system, in beaker, drip 0.1g coordination platinum catalyst again control water temperature ultrasonic disperse 1h at 30 DEG C, there will be obvious crosslinking phenomena.Utilize water pump to carry out application of vacuum to it to above-mentioned solution 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.
By prefabricated post in Muffle furnace, be warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treat removing template, namely obtain the required integral post with through-hole structure.
Embodiment 3
In the present embodiment, the preparation process of polystyrene microsphere is with embodiment one.Unlike: weigh 1g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic disperse 15min dissolves completely to polystyrene, each mixed solution by 5gPHMS and 5gD4Vi joins in beaker afterwards, continue ultrasonic disperse 30min and form dispersed system, in beaker, drip 0.1g coordination platinum catalyst again control water temperature ultrasonic disperse 1h at 30 DEG C, there will be obvious crosslinking phenomena.Utilize water pump to carry out application of vacuum to it to above-mentioned solution 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.
By prefabricated post in Muffle furnace, be warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treat removing template, namely obtain the required integral post with through-hole structure.
Embodiment 4
In the present embodiment, the preparation process of polystyrene microsphere is with embodiment one.Unlike: weigh 0.5g polystyrene microsphere and be dissolved in 3g ethanol, ultrasonic disperse 15min dissolves completely to polystyrene, each mixed solution by 5gPHMS and 5gD4Vi joins in beaker afterwards, continue ultrasonic disperse 30min and form dispersed system, in beaker, drip 0.1g coordination platinum catalyst again control water temperature ultrasonic disperse 1h at 30 DEG C, there will be obvious crosslinking phenomena.Utilize water pump to carry out application of vacuum to it to above-mentioned solution 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.
By prefabricated post in Muffle furnace, be warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treat removing template, namely obtain the required integral post with through-hole structure.
Embodiment 5
The present embodiment is blank test, by 3g EtOH Sonicate dispersion 15min, each mixed solution by 5gPHMS and 5gD4Vi joins in beaker afterwards, continue ultrasonic disperse 30min and form dispersed system, in beaker, drip 0.1g coordination platinum catalyst again control water temperature ultrasonic disperse 1h at 30 DEG C, there will be obvious crosslinking phenomena.Utilize water pump to carry out application of vacuum to it to above-mentioned solution 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.
By prefabricated post in Muffle furnace, be warming up to 750 DEG C of constant temperature 30min with the speed of 3 DEG C/min and heat-treat, namely obtain the required integral post with through-hole structure.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (4)
1. Silica gel monolithic column for HPLC, it is characterized in that, utilize polystyrene microsphere as template, hydrogen containing siloxane and t etram-ethyltetravinylcyclotetrasiloxane are carried out in-situ cross-linkedly obtain prefabricated post, carry out according to following step: take 0.5-2 mass fraction polystyrene microspheres in ethanol dispersed, the hydrogen containing siloxane of mass fraction and the t etram-ethyltetravinylcyclotetrasiloxane such as then to add and be dispersed into homogeneous system, ultrasonic disperse mode is selected to disperse above-mentioned system, add coordination platinum catalyst wherein again, methyl vinyl silicone coordination platinum catalyst selected by described coordination platinum catalyst, its chemical formula is as follows:
Described catalyst charge is 1%-3% of hydrogen containing siloxane and t etram-ethyltetravinylcyclotetrasiloxane gross mass, control temperature proceeds dispersion at being 20-30 DEG C, until after there is crosslinking phenomena, be injected in mould and can obtain prefabricated post at 50-80 DEG C of heating 4-12h, polystyrene microsphere in recycling high temperature removing prefabricated post, the chromatography silica gel integral post with through-hole structure can be obtained, there is through-hole structure, pass is more even, pore diameter range concentrates on 30-35nm, specific area 500-550m
2/ g, have macropore and central hole structure, porosity is greater than 80% simultaneously.
2. Silica gel monolithic column for HPLC according to claim 1, is characterized in that, after there is crosslinking phenomena, after selecting pump to carry out the residual etoh solvent of application of vacuum removal to system, then carries out injection mould; The needs that described mould uses according to reality are processed, with the requirement making the prefabricated post of preparation substantially meet shape size in actual use; Be injected into after in mould, at 60-70 DEG C of heating 6-10h, to meet the needs completing crosslinked and abundant solvent flashing ethanol as far as possible.
3. Silica gel monolithic column for HPLC according to claim 1, it is characterized in that, after the preparation having carried out prefabricated post, prefabricated post is placed in Muffle furnace, be warming up to 750 DEG C of constant temperature 60min with the speed of 3 DEG C/min from room temperature 20-25 DEG C and heat-treat removing template, namely obtain the required integral post with through-hole structure.
4. the preparation method of Silica gel monolithic column for HPLC, it is characterized in that, utilize polystyrene microsphere as template, described polystyrene microsphere selects the polystyrene microsphere often selected in method for preparing template, hydrogen containing siloxane and t etram-ethyltetravinylcyclotetrasiloxane are carried out in-situ cross-linkedly obtain prefabricated post, carry out according to following step: take 0.5-2 mass fraction polystyrene microspheres in ethanol dispersed, the hydrogen containing siloxane of mass fraction and the t etram-ethyltetravinylcyclotetrasiloxane such as then to add and be dispersed into homogeneous system, ultrasonic disperse mode is selected to disperse above-mentioned system, add coordination platinum catalyst wherein again, methyl vinyl silicone coordination platinum catalyst selected by described coordination platinum catalyst, its chemical formula is as follows:
Described catalyst charge is 1%-3% of hydrogen containing siloxane and t etram-ethyltetravinylcyclotetrasiloxane gross mass, control temperature proceeds dispersion at being 20-30 DEG C, until after there is crosslinking phenomena, after selecting pump to carry out the residual etoh solvent of application of vacuum removal to system, then carry out injection mould; The needs that described mould uses according to reality are processed, with the requirement making the prefabricated post of preparation substantially meet shape size in actual use; Be injected into after in mould, at 60-70 DEG C of heating 6-10h, to meet the needs completing crosslinked and abundant solvent flashing ethanol as far as possible, be injected in mould and can obtain prefabricated post at 50-80 DEG C of heating 4-12h, prefabricated post is placed in Muffle furnace, be warming up to 750 DEG C of constant temperature 60min with the speed of 3 DEG C/min from room temperature 20-25 DEG C and heat-treat removing template, the chromatography silica gel integral post with through-hole structure can be obtained, there is through-hole structure, pass is more even, pore diameter range concentrates on 30-35nm, specific area 500-550m
2/ g, have macropore and central hole structure, porosity is greater than 80% simultaneously.
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| CN102314559A (en) * | 2011-10-19 | 2012-01-11 | 天津大学 | Method for predicting retention time of gas phase chromatogram based on macromolecule crystallization behavior derivation retention equation |
| CN102507812A (en) * | 2011-09-26 | 2012-06-20 | 天津大学 | Method for forecasting retention time of double-column series gas chromatogram |
| 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 |
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| CN102507812A (en) * | 2011-09-26 | 2012-06-20 | 天津大学 | Method for forecasting retention time of double-column series gas chromatogram |
| CN102314559A (en) * | 2011-10-19 | 2012-01-11 | 天津大学 | Method for predicting retention time of gas phase chromatogram based on macromolecule crystallization behavior derivation retention equation |
| 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 |
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