CN105126388B - A kind of preparation method of monolithic silica column - Google Patents
A kind of preparation method of monolithic silica column Download PDFInfo
- Publication number
- CN105126388B CN105126388B CN201510406670.8A CN201510406670A CN105126388B CN 105126388 B CN105126388 B CN 105126388B CN 201510406670 A CN201510406670 A CN 201510406670A CN 105126388 B CN105126388 B CN 105126388B
- Authority
- CN
- China
- Prior art keywords
- gel
- mesopore
- silica column
- water
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of monolithic silica column.It is that, using silica hydrosol as silicon source, methyl silicate is crosslinking agent, and polyethylene glycol is pore-foaming agent, and collosol and gel is carried out in alkaline environment.After after pillar gel, with the ammoniacal liquor, distilled water, N of various concentrations, N dimethylformamides are eluted successively, are then dried, are calcined with Muffle furnace in vacuum drying chamber.The monolithic silica column of preparation has micron-sized skeleton, through hole and nano level mesopore simultaneously, and the presence of wherein through hole makes monolithic silica column have very strong permeability, and the change of post pressure drop with flow rate is smaller；Mesopore then provides larger specific surface area for integral post, is the precondition for ensureing its Gao Zhuxiao.By adjusting the proportion of composing of reactant, the aperture of through hole and mesopore can be independently controlled, skeleton average-size is 1~2 μm, through hole average-size is 2~3 μm, the average-size for testing mesopore through nitrogen adsorption desorption is 20nm, and its pore volume is conducive to industrialization development than filling pillar height.
Description
Technical field
The present invention is to utilize Ludox for silicon source under alkaline environment, and prepare has micron order skeleton, through hole and receive simultaneously
The integral post of meter level mesopore, the utilization alkoxysilane reagent reported for work hydrolytie polycondensation in acid condition is former with saving
Material, it is nontoxic, the advantages of simple and fast.
Background technology
From after Russia botanist TSwett in 1903 has found chromatogram, with continuing to develop and progressive for science, chromatogram
Technology is developed rapidly in each scientific domain, has been widely used in material science, environmental science, life science, information
The directions such as science.Chromatographic column, in order to adapt to the progress of science and technology, is also sent out forward as the core of chromatographic technique constantly
Exhibition.Current existing chromatographic technique can meet the requirement of every field substantially, but the particular/special requirement of bio-chemistry separation, new drug development and
The research of the further investigation of genome, especially combinatorial chemistry and proteomics, be badly in need of efficiently, high selectivity, quick separating with
The chromatographic column of the requirements such as detection.
Monolithic Columns are a kind of new structural materials that the eighties, Later development got up, and it is by in-situ polymerization or solid
The continuous bar-shaped entirety with loose structure that fixedization is formed in column jecket.Integral post have prepare simple, consistent internal structure,
Favorable reproducibility, low pressure, quickly, the advantages of efficient, and can be chemically modified to its surface, be after packed column as needed
What another was new afterwards is used to separate analysis or as the porous media of reactor, and it acts not only as micro column liquid chromatography
With the stationary phase of capillary electric chromatogram, and the carrier of example enrichment and enzyme reactor is may be used as, thus by more and more
Concern.
Monolithic silica column is a kind of chromatograph packing material that nineteen nineties new development is got up, with low pressure, quick, height
The advantages of effect, high mechanical strength and column performance are stable, has very wide application prospect in fields such as catalysis, synthesis, separation.But by
Higher in the difficulty of its synthetic technology, only this technology is grasped in a few experiments room at present.Therefore, research and develop general, practical
Monolithic silica column has important practical significance.
The content of the invention
For above-mentioned situation, the problem of present invention is intended to solve is to provide one kind in the basic conditions, based on Ludox
The method for wanting raw material to prepare monolithic silica column, can prepare no fracture, shrinkage-free high-efficient silica gel integral post.
The invention discloses a kind of preparation method of new monolithic silica column, it be using silica hydrosol as silicon source,
Methyl silicate is crosslinking agent, and polyethylene glycol is pore-foaming agent, and sol gel is carried out in alkaline environment.Treat pillar gel, it is old
After change, eluted, soaked, then in vacuum drying chamber successively with the ammoniacal liquor, distilled water, DMF of various concentrations
Drying, carries out calcine by steps in Muffle furnace.The monolithic silica column prepared using this method is while having micron-sized skeleton, leading to
Hole and nano level mesopore.Wherein, the presence of through hole makes monolithic silica column have very strong permeability, and post pressure drop with flow rate becomes
Change smaller；Mesopore then provides larger specific surface area for integral post, is the precondition for ensureing its Gao Zhuxiao.
A kind of preparation method of monolithic silica column, is comprised the following steps that：
A. in the there-necked flask equipped with agitating device, silica gel is added, and add the poly- second that molecular weight is 2000-10000
Glycol, stirring, treats that it is completely dissolved, and forms homogeneous phase solution, then will be installed on temperature in 0 DEG C~5 DEG C ice-water baths, to be added dropwise
Distilled water, the pH of regulation system is 9 ± 0.5, and methyl silicate is added dropwise, the mol ratio of the water silicon of system is maintained 10-
15, its complete hydrolysis afterloading tube in system, Sealing jaw two-port are treated in stirring.
B. the integral post prepared in above-mentioned A is placed in water-bath and carries out collosol and gel, ageing 24h, torn open after after pillar gel
Except two ends diaphragm seal, soak 1-3 hour to prepare mesopore with the ammoniacal liquor of 0.01mol/L-1mol/L various concentrations successively, then
With 1-2 hour of distilled water immersion.Add N,N-dimethylformamide and soak 1-5 hour.
C. processing is dried in the integral post after being handled in above-mentioned B, 1- is dried in prior to 30-45 DEG C vacuum drying chamber
3h, is then gradually heating to 50-60 DEG C and continues to dry 7-9h.Calcined in Muffle furnace.
Further, calcining heating schedule is：25 DEG C to 100 DEG C of room temperature is heated up with 1 DEG C/min speed, 100 DEG C of insulations
1h, 100 DEG C to 350 DEG C are heated up with 2 DEG C/min speed, 350 DEG C of insulation 1h, and 350 DEG C to 700 DEG C are entered with 4 DEG C/min speed
Row heating, 700 DEG C of insulation 2h.
Further, as silicon source, silica gel provides 60-80% silicon, and remaining 20-40% is provided by methyl silicate.
Before it is dried, because being full of water in cylinder hole, and the surface tension of water is very high, makes silicagel column easy in drying process
Ftracture.In order to eliminate cracking phenomena, before drying, low volatility, the N of low surface tension, N- dimethyl are added in system
Formamide soaks 5 hours.When drying, what is first volatilized away is the material of the high volatility such as water, remaining to be only surface tension
The material of low, low volatility, such rate of drying is effectively controlled, and cracking phenomena is eliminated.
In order to further avoid that 1- is dried in the cracking for drying ageing process middle column body, prior to 30-45 DEG C vacuum drying chamber
3h, is then gradually heating to 50-60 DEG C and continues to dry 7-9h.Carry out calcine by steps in Muffle furnace, processing machinery intensity it is big and
Monolithic silica column with double-pore structure.
The beneficial effects of the invention are as follows：
1st, the crosslinking agent methyl silicate added in the present invention, surface is connected with substantial amounts of hydroxyl after hydrolyzing in the basic conditions
Base, being capable of the efficient hydroxyl generation polycondensation with Ludox surface, formation network structure, due to depositing for perforating agent polyethylene glycol
Uniform skeleton and through hole can be being formed after gel, ageing, drying, calcining.
2nd, the present invention prepares shorter monolithic silica column and preferably can shunk controlled fracturing blasting, by two shorter integral posts
Comparatively ideal separating effect can be realized in series connection access analysis chromatogram.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of embodiment one
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of embodiment two
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of embodiment three
Fig. 4 is TG-DTA (TG-DTA) analysis chart before monolithic silica column calcining
Fig. 5 is the macrograph after monolithic silica column calcining
Embodiment
Embodiment one
A. in the there-necked flask equipped with agitating device, solid content is 25% silica gel 44.77g, and it is pure to add 3.64g analyses
After polyethylene glycol, stirring 20min, treat that it is completely dissolved, form homogeneous phase solution, then it is 0 DEG C~5 DEG C ice-water baths that will be installed on temperature
In, distilled water is added dropwise, the pH of regulation system is 9, continues to stir after 10min, and the pure methyl silicate of analysis is added dropwise
After 3.1mL, stirring 15min, its complete hydrolysis afterloading tube in system, Sealing jaw two-port are treated.
B. treat that the integral post prepared in above-mentioned A is placed in 40 DEG C of water-baths and carry out collosol and gel, ageing 24h, treat pillar gel
Two ends diaphragm seal is removed afterwards, pillar is placed in larger culture dish, successively with 0.01mol/L, 0.1mol/L, 1mol/L ammoniacal liquor
Respectively 3 hours of immersion prepare mesopore to 200mL, then with 2 hours of 200mL distilled water immersions, before drying, then with low volatility, low
The N,N-dimethylformamide 200mL of surface tension soaks 5 hours.
C. processing is dried in the integral post after being handled in above-mentioned B, 3h is dried in prior to 45 DEG C vacuum drying chambers, then
60 DEG C are gradually heating to continue to dry 9h.Put vacuum and take out dried pillar, calcine by steps is carried out in Muffle furnace, according to silicon
The differential thermal analysis temperature programming of glue integral post is：25 DEG C to 100 DEG C of room temperature is heated up with 1 DEG C/min speed, 100 DEG C of insulations
1h, 100 DEG C to 350 DEG C are heated up with 2 DEG C/min speed, 350 DEG C of insulation 1h, and 350 DEG C to 700 DEG C are entered with 4 DEG C/min speed
Row heating, 700 DEG C of insulation 2h.
Embodiment two
A. in the there-necked flask equipped with agitating device, solid content is 25% silica gel 39.8g, and it is pure to add 3.64g analyses
After polyethylene glycol, stirring 20min, treat that it is completely dissolved, form homogeneous phase solution, then it is 0 DEG C~5 DEG C ice-water baths that will be installed on temperature
In, distilled water is added dropwise, the pH of regulation system is 9, continues to stir after 10min, and the pure methyl silicate of analysis is added dropwise
After 6.2mL, stirring 15min, its complete hydrolysis afterloading tube in system, Sealing jaw two-port are treated.
B. treat that the integral post prepared in above-mentioned A is placed in 40 DEG C of water-baths and carry out collosol and gel, ageing 24h, treat pillar gel
Two ends diaphragm seal is removed afterwards, pillar is placed in larger culture dish, successively with 0.01mol/L, 0.1mol/L, 1mol/L ammoniacal liquor
Respectively 3 hours of immersion prepare mesopore to 200mL, then with 2 hours of 200mL distilled water immersions, before drying, then with low volatility, low
The N,N-dimethylformamide 200mL of surface tension soaks 5 hours.
C. processing is dried in the integral post after being handled in above-mentioned B, 3h is dried in prior to 45 DEG C vacuum drying chambers, then
60 DEG C are gradually heating to continue to dry 9h.Put vacuum and take out dried pillar, calcine by steps is carried out in Muffle furnace, according to silicon
The differential thermal analysis temperature programming of glue integral post is：25 DEG C to 100 DEG C of room temperature is heated up with 1 DEG C/min speed, 100 DEG C of insulations
1h, 100 DEG C to 350 DEG C are heated up with 2 DEG C/min speed, 350 DEG C of insulation 1h, and 350 DEG C to 700 DEG C are entered with 4 DEG C/min speed
Row heating, 700 DEG C of insulation 2h.
Embodiment three
A. in the there-necked flask equipped with agitating device, addition solid content is 25% silica gel 34.8g, and adds 3.64g points
Analyse after pure polyethylene glycol, stirring 20min, treat that it is completely dissolved, form homogeneous phase solution, then it is 0 DEG C~5 DEG C ice that will be installed on temperature
In water-bath, distilled water is added dropwise, the pH of regulation system is 9, continues to stir after 10min, and the pure silicic acid first of analysis is added dropwise
After ester 9.3mL, stirring 15min, its complete hydrolysis afterloading tube in system, Sealing jaw two-port are treated.
B. treat that the integral post prepared in above-mentioned A is placed in 40 DEG C of water-baths and carry out collosol and gel, ageing 24h, treat pillar gel
Two ends diaphragm seal is removed afterwards, pillar is placed in larger culture dish, successively with 0.01mol/L, 0.1mol/L, 1mol/L ammoniacal liquor
Respectively 3 hours of immersion prepare mesopore to 200mL, then with 2 hours of 200mL distilled water immersions, before drying, then with low volatility, low
The N,N-dimethylformamide 200mL of surface tension soaks 5 hours.
C. processing is dried in the integral post after being handled in above-mentioned B, 3h is dried in prior to 45 DEG C vacuum drying chambers, then
60 DEG C are gradually heating to continue to dry 9h.Put vacuum and take out dried pillar, calcine by steps is carried out in Muffle furnace, according to silicon
The differential thermal analysis temperature programming of glue integral post is：25 DEG C to 100 DEG C of room temperature is heated up with 1 DEG C/min speed, 100 DEG C of insulations
1h, 100 DEG C to 350 DEG C are heated up with 2 DEG C/min speed, 350 DEG C of insulation 1h, and 350 DEG C to 700 DEG C are entered with 4 DEG C/min speed
Row heating, 700 DEG C of insulation 2h.
Claims (2)
1. a kind of preparation method of monolithic silica column, is comprised the following steps that：
A. in the there-necked flask equipped with agitating device, add silica gel, and add molecular weight be 2000-10000 polyethylene glycol,
Stirring, treats that it is completely dissolved, and forms homogeneous phase solution, then will be installed on temperature in 0 DEG C~5 DEG C ice-water baths, distillation is added dropwise
Water, the pH of regulation system is 9 ± 0.5, and methyl silicate is added dropwise, the mol ratio of the water silicon of system is maintained 10-15, stirs
Mix, treat its complete hydrolysis afterloading tube in system, Sealing jaw two-port；
B. the integral post prepared in above-mentioned A is placed in water-bath and carries out collosol and gel, ageing 24h, after removing two after pillar gel
Diaphragm seal is held, soaks 1-3 hour with the ammoniacal liquor of 0.01mol/L-1mol/L various concentrations successively to prepare mesopore, then with steaming
Distilled water soaks 1-2 hour；Add N,N-dimethylformamide and soak 1-5 hour；
C. processing is dried in the integral post after being handled in above-mentioned B, 1-3h is dried in prior to 30-45 DEG C vacuum drying chamber, so
After be gradually heating to 50-60 DEG C continue dry 7-9h；Calcined in Muffle furnace.
2. preparation method according to claim 1, it is characterised in that：Calcining heating schedule is：25 DEG C to 100 DEG C of room temperature
Heated up with 1 DEG C/min speed, 100 DEG C of insulation 1h, 100 DEG C to 350 DEG C are heated up with 2 DEG C/min speed, 350 DEG C of insulations
1h, 350 DEG C to 700 DEG C are heated up with 4 DEG C/min speed, 700 DEG C of insulation 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510406670.8A CN105126388B (en) | 2015-07-12 | 2015-07-12 | A kind of preparation method of monolithic silica column |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510406670.8A CN105126388B (en) | 2015-07-12 | 2015-07-12 | A kind of preparation method of monolithic silica column |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105126388A CN105126388A (en) | 2015-12-09 |
| CN105126388B true CN105126388B (en) | 2017-07-18 |
Family
ID=54712171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510406670.8A Active CN105126388B (en) | 2015-07-12 | 2015-07-12 | A kind of preparation method of monolithic silica column |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105126388B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109865497A (en) * | 2019-04-02 | 2019-06-11 | 青岛硕远硅胶科技有限公司 | A kind of preparation method of high-purity porous spherical silica filler |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205476C (en) * | 2003-08-29 | 2005-06-08 | 武汉大学 | Open tucular column or silica integral column with propyl sulphonic ion coating and preparation and use thereof |
| ITRM20060723A1 (en) * | 2006-12-29 | 2008-06-30 | Avantech Group S R L | HIGH PERFORMANCE CHROMATOGRAPHIC COLUMNS CONTAINING ORGANIC OR COMPOSITE POLYMERIC MONOLITHIC SUPPORTS AND RELATED PREPARATION METHOD. |
| GB0707375D0 (en) * | 2007-04-17 | 2007-05-23 | Univ Greenwich | Solid phase extraction of ochratoxins |
| CN102636602B (en) * | 2012-04-12 | 2014-04-09 | 福州大学 | Neutral hydrophilically-interacted hybrid silicagel-based monolithic column |
| CN104338344A (en) * | 2013-07-26 | 2015-02-11 | 瞿其曙 | Particle type monolithic column preparation method |
| CN104258805A (en) * | 2014-09-16 | 2015-01-07 | 天津大学 | Preparation method of hybridized silica gel monolithic column |
-
2015
- 2015-07-12 CN CN201510406670.8A patent/CN105126388B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105126388A (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101590394B (en) | Preparation method and use of molecular imprinting-absorbing extraction stirring rod | |
| CN102166434B (en) | Mesoporous material coating based open-tubular capillary chromatographic column and preparation method thereof | |
| CN109621911A (en) | A kind of SPME extracting fiber of porous organic framework coating and preparation method thereof | |
| Liu et al. | Polymer-modified fibrous mesoporous silica nanoparticles as coating material for open-tubular capillary electrochromatography | |
| CN102091604A (en) | MOFs material-based series molecular sieve and preparation method and application method thereof in complex sample purification and separation analysis | |
| CN1213799C (en) | Sequential porous silica gel whole column and its preparation and use | |
| CN104861130A (en) | Polymer brush graft boracic acid affinity separation material and preparation method and application | |
| CN107875672A (en) | Micro-extraction for solid adsorption material stirs bar device and its application method | |
| CN108654322A (en) | A kind of preparation method and application based on alkaline functional ionic liquid blend film | |
| CN103551131A (en) | Preparation method of polypropylene film micro solid-phase extraction packet based on MIL-101 adsorbent | |
| CN109092275A (en) | A kind of preparation method of the alkyl linked silica filler of novel hydrophilic | |
| CN102416313A (en) | Bisphenol A dummy template molecularly imprinted stir bar and preparation method thereof | |
| CN105126388B (en) | A kind of preparation method of monolithic silica column | |
| CN106966973A (en) | N phenyl N（The quinolyl of 2 methyl 8）The preparation method of benzamide | |
| CN107262077B (en) | A kind of preparation method being bonded organic polymer overmold silicon ball chromatographic stationary phases | |
| CN105561958B (en) | Ionic liquid bonded silica gel for enrichment and purification of shellfish toxins and preparation method thereof | |
| CN111333074A (en) | Method for preparing mesoporous silicon oxide by using biomass as raw material and application thereof | |
| CN102872613B (en) | Preparation method of organic-inorganic hybridization monolithic column | |
| CN104606919B (en) | Preparation method of nucleic acid aptamer/nano-gold modified solid phase microextraction quartz capillary tube | |
| CN104557718B (en) | A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material | |
| CN109158095A (en) | A kind of filling column packing and preparation method thereof | |
| CN106268712B (en) | A kind of method of preparation and use of the micro-extraction carbon-point based on surface molecule print | |
| CN105921116B (en) | Cation with immixture pattern exchanges Solid Phase Extraction material and its preparation method and application | |
| CN103611510A (en) | Preparation method of non-woven fabric micro-solid phase extraction bag based on MIL-101 adsorbent | |
| CN107261558A (en) | A kind of chromatographic column and its preparation method of stationary phase based on graphite alkenes Yu zinc oxide duplicature stationary phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |