CN105056875B - The preparation method of zirconium oxide integral post - Google Patents
The preparation method of zirconium oxide integral post Download PDFInfo
- Publication number
- CN105056875B CN105056875B CN201510439874.1A CN201510439874A CN105056875B CN 105056875 B CN105056875 B CN 105056875B CN 201510439874 A CN201510439874 A CN 201510439874A CN 105056875 B CN105056875 B CN 105056875B
- Authority
- CN
- China
- Prior art keywords
- integral post
- gel
- zirconium
- peg
- water
- 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.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of preparation method of zirconium oxide integral post, belong to technical field of chemistry, this method comprises the following steps：(1) preparation of wet gel：Weigh appropriate PEG and absolute ethyl alcohol is fitted into round-bottomed flask, it is put into water-bath to mix to PEG and all dissolves, cool down and sequentially add zirconium-n-propylate, glacial acetic acid, the concentrated sulfuric acid in backward flask, it is subsequently adding magneton, after being stirred on magnetic stirring apparatus, colloidal sol is obtained, the colloidal sol is placed in gel in water-bath, by the wet cylinder water-bath ageing of gained after gel；(2) urea ethanol solution heat treatment；(3) integral post is dried；(4) Muffle furnace calcination.The characteristics of integral post filler high mechanical strength of the present invention, good stability, can effectively prevent chromatographic column from collapsing, and overall column packing energy fabricated in situ, it ensure that the reappearance of integral post, reliability and service life.
Description
Technical field
The invention belongs to technical field of chemistry, and in particular to a kind of preparation method of zirconium oxide integral post.
Background technology
Chromatographic column is the core of chromatographic technique, and chromatographic column filler affects the range of application of chromatogram.
At present, the chromatographic column filler with silica gel as matrix accounts for more than 80%, but, the applicable pH models of silica gel base fixing phase
Narrow (pH=2~8) are enclosed, and basicity is excessive, and particularly in the presence of quaternary ammonium ion, silica gel is easy to crush dissolving.Additionally can
Irreversible Adsorption is produced to biological sample, therefore limits application of the silica gel base in some key areas.It is, thus, sought for
A kind of liquid chromatography stuffing of alkali resistance.
Zirconium dioxide is a kind of alkalescent oxide, its excellent chemical stability, heat endurance and high mechanical properties, closely
Extensive concern is received over year, the research on zirconium dioxide column packing is more and more.Zirconium dioxide is to aqueous slkali and many
Acid solution all has enough stability, and the pH scopes of application are pH=l~14, and the separation to alkaline matter is extremely advantageous,
And with special selectivity, good performance can be formed with silica filler complementary.In addition, zirconium dioxide intensity is high, high temperature resistant,
Therefore it can overcome the disadvantages that some shortcomings of silica gel and organic polymer fillers so that it has in fields such as biochemistry, medical industries
Important application, can be used for the separation of biomolecule such as amino acid, peptide, protein, nucleosides, monoclonal antibody；Alkyl is replaced
Benzene, aromatic hydrocarbon, the separation of polynuclear aromatic hydrocarbons also have been reported that；The ion-exchange chromatography determined for anion, cation is also zirconium base
One important application aspect of chromatograph packing material；The application that zirconium dioxide separation aspect also under extreme conditions shows uniqueness is preceding
Scape.Therefore zirconium dioxide and modified zirconium dioxide chromatograph packing material have obtained more and more many, more and more important applications.
At present, with zirconium dioxide as matrix chromatographic column filler is most based on high-purity spheric granules, but is using
During particles filled type chromatographic column, easily " collapsing ", chromatographic column inner stuffing has the possibility of " cutout " or " short stream " to chromatogram column cap.
The content of the invention
One of the object of the invention is to solve existing chromatogram column cap easily " collapsing ", and chromatographic column inner stuffing has " cutout "
Or the problem of " short stream ", there is provided a kind of preparation method of zirconium oxide integral post.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of zirconium oxide integral post, this method comprises the following steps：(1) preparation of wet gel：Weigh suitable
Amount PEG and absolute ethyl alcohol are fitted into round-bottomed flask, are put into water-bath to mix to PEG and all dissolve, in the backward flask of cooling
Zirconium-n-propylate, glacial acetic acid, the concentrated sulfuric acid are sequentially added, magneton is subsequently adding, after being stirred on magnetic stirring apparatus, colloidal sol is obtained, by institute
State colloidal sol and be placed in gel in water-bath, by the wet cylinder water-bath ageing of gained after gel；(2) urea ethanol solution heat treatment：With one
The urea ethanol solution for determining concentration is heat-treated the wet gel cylinder after the ageing；(3) integral post is dried：After making the heat treatment
Cylinder dry；(4) Muffle furnace calcination：Dried integral post is taken out, calcination in Muffle furnace is put into.
Further, the zirconium-n-propylate and the mass ratio of the concentrated sulfuric acid are 1.64/0.075~1.64/0.28.
Further, the zirconium-n-propylate and the concentrated sulfuric acid mass ratio are 1.64/0.16.
Further, the zirconium-n-propylate and the mass ratio of the PEG are 1.64:0.04.
Further, the temperature parameter of heat treatment is 120 DEG C in the step (2).
Further, the concentration of the urea ethanol solution is 0.2~0.5_molL-1。
Further, the concentration of the urea ethanol solution is 0.5molL-1。
Further, the mol ratio of the zirconium-n-propylate, the acetic acid and the absolute ethyl alcohol is 1:3:3.
The beneficial effects of the present invention are, integral post filler high mechanical strength prepared in accordance with the present invention, good stability
Feature can effectively prevent chromatographic column from collapsing；Traditional silica gel particle filler is compared, Monolithic Columns inside has micron-sized passing through
Perforation so that mobile phase can be flowed quickly through inside integral post at low pressures, and silica gel particle is instead of with convective mass transfer
Diffusion mass transfer, is capable of achieving efficient quick separating；And overall column packing energy fabricated in situ, it ensure that the reappearance of integral post,
Reliability and service life.
Specific embodiment
In zirconium oxide integral post preparation process, hydrolysis and polycondensation reaction as follows is mainly there occurs：
Hydrolysis：
Polymerisation：
Condensation reaction：
Wherein, poly-condensation and hydrolysis are a pair while the competitive reaction for carrying out.Zirconium-n-propylate is easily hydrolyzed, micro- in air
The water of amount just can hydrolyze it and form the precipitation of particle packing, so the hydrolysis rate of control zirconium alkoxide is crucial, this hair
The minor amount of water catalyzing hydrolysis that bright use esterification is produced, allow hydrolysis condensation reaction slowly to carry out, and the amount of the concentrated sulfuric acid influences
The speed of hydrolysis, so as to influence the synthesis speed of gel.
With the carrying out of reaction, PEG forms stronger hydrogen bond action, its conjugate and body with the Zr-OH of gel oligomer
The intermiscibility of system declines, and is separated, and gradually forms gel oligomer rich with the gel enrichment phase and solvent of PEG combinations
Collection phase, while the viscosity increase of system, and reaches gelation, its solid phase (gel oligomer and PEG conjugates) with ageing gradually
Roughening, growth, ultimately form the mesh skeleton structure of stabilization.After wet gel is thermally treated and dry, calcination forms zirconium dioxide
Integral post.
The preparation method of zirconium oxide integral post comprises the following steps：
(1) prepared by wet gel
Weigh appropriate PEG (10000) and absolute ethyl alcohol is fitted into round-bottomed flask, be put into 60 DEG C of water-baths and mix to PEG
All dissolvings, zirconium-n-propylate, glacial acetic acid, the concentrated sulfuric acid are sequentially added in the backward flask of cooling, add magneton, are placed on magnetic stirring apparatus
Upper stirring 20min, colloidal sol is distributed into 5 moulds of 4cm, is placed on gel in 40 DEG C of water-baths, by gel after wet post
Body is placed in 40 DEG C and 60 DEG C of water-baths are successively aged 24h.
(2) urea ethanol solution heat treatment
Wet wet gel cylinder after by ageing is removed from the molds, and is heat-treated with certain density urea ethanol solution, temperature
120 DEG C of degree, time 24h.
(3) integral post is dried
Cylinder after heat treatment is taken out from reactor, is placed in 50 DEG C of baking ovens and is dried, drying time 24h.
(4) Muffle furnace calcination
Dried integral post is taken out, calcination in Muffle furnace is put into.Heating schedule is set：
The present invention is described in detail below in conjunction with specific embodiment.It should be noted that the skill described in following embodiments
The combination of art feature or technical characteristic be not construed as it is isolated, they can be mutually combined so as to reach preferably
Technique effect.
Embodiment 1
Take six round-bottomed flasks, number consecutively 1,2,3,4,5,6.With reference to table 1, PEG (10000), anhydrous second are weighed respectively
Alcohol is fitted into round-bottomed flask, is put into 60 DEG C of water-baths to PEG and all dissolves, and to cool down and sequentially add normal propyl alcohol in backward flask
Zirconium, glacial acetic acid, 0.08~0.28g concentrated sulfuric acids, add magneton, be placed on and 20min is stirred on magnetic stirring apparatus, and colloidal sol is distributed into 6
In the mould of individual 4cm, be placed on gel in 40 DEG C of water-baths, by gel after wet cylinder be placed in 40 DEG C and 60 DEG C of water-baths are respectively aged
24h。
Table 1
Note：The numbering that 1-1 is expressed as table 1 is 1 flask, and other numberings are similar.
The speed of concentrated sulfuric acid control esterification, and then the speed of hydrolysis condensation reaction is influenceed, referring to table 1, work as the concentrated sulfuric acid
Amount it is less when, by after ageing, colloidal sol bottom separates out precipitation；Gradually increase the amount of the concentrated sulfuric acid, cylinder can be formed, and dry post
The shrinkage factor of body is gradually reduced；When the amount of the concentrated sulfuric acid is excessive, gradually decreased the time required to reaching phase separation, it is last directly to burn
Clear gel is just formed in bottle.Amid all these factors, during the zirconium-n-propylate/concentrated sulfuric acid=1.64/0.16 (mass ratio) left and right, cylinder
Molding effect is preferable.
Embodiment 2
Four round-bottomed flasks are taken, successively label 1,2,3,4,5.With reference to table 2,0.02~0.06g PEG are weighed respectively
(10000), absolute ethyl alcohol is fitted into round-bottomed flask, is put into 60 DEG C of water-baths to PEG and all dissolves, cool down in backward flask according to
Secondary addition zirconium-n-propylate, glacial acetic acid, the concentrated sulfuric acid, add magneton, be placed on and 20min is stirred on magnetic stirring apparatus, and colloidal sol is distributed into 5
In the mould of individual 4cm, be placed on gel in 40 DEG C of water-baths, by gel after wet cylinder be placed in 40 DEG C and 60 DEG C of water-baths are respectively aged
24h.The specific data of used chemicals are shown in Table 2.
Table 2
Note：The numbering that 2-1 is expressed as table 1 is 1 flask, and other numberings are similar.
Referring to table 2, with the increase that PEG is measured, slave phase increases the time required to being separated to gel point, and when PEG amounts are excessive,
Cannot be dissolved in the ethanol of fixed amount, and after phase separation, gel is slowly changed into precipitation.Consider, as zirconium-n-propylate/PEG
During=1.64/0.04 (g/g) left and right, it is separated more long to the time of gel point, can forms that shrinkage factor is small, the entirety of any surface finish
Post, and cylinder shaping is preferable.
The addition of PEG can improve the uniformity of colloid, and PEG plays catalyst and cause in zirconium dioxide integral post preparation process
The effect of hole agent.PEG in reaction system can induce be separated generation so that in reaction system formed polymer rich phase and
PEG solution enrichment phases.In addition, there are numerous ehter bonds in PEG molecules, adsorb in zirconium dioxide colloid substrate surface, by follow-up
Calcination is processed, and PEG is removed, so as to leave corresponding micron order macropore and nano level bone frame aperture pore passage structure.With PEG concentration
Increase, adsorb many in the PEG quantitative changes of zirconium dioxide colloid group, when the concentration of PEG in solution reaches to a certain degree, PEG point
Subchain, toward reuniting, forms PEG micelles from full extension, and PEG micelles serve as pore-foaming agent in system, and the concentration of PEG is bigger,
The skeleton aperture of zirconium dioxide integral post is bigger, and specific surface reduces, and the specific surface of zirconium dioxide integral post declines and pore volume increases
Plus.
Embodiment 3
With reference to table 3,0.2g PEG (10000) are weighed, 3.476g absolute ethyl alcohols are fitted into round-bottomed flask, are put into 60 DEG C of water-baths
All dissolved to PEG in pot, 8.20g zirconium-n-propylates, 4.515g glacial acetic acids, the dense sulphur of 0.79g are sequentially added in the backward flask of cooling
Acid, add magneton, be placed on and 20min stirred on magnetic stirring apparatus, colloidal sol is distributed into 4 moulds of 4cm, respectively label 1,2,
3、4.Be placed on gel in 40 DEG C of water-baths, by gel after wet cylinder be placed in 40 DEG C and 60 DEG C of water-baths are respectively aged 24h.
Wet cylinder after by ageing is removed from the molds, every respectively with 0.2,0.3,0.4, the urea ethanol of 0.5mol/L
Solution is heat-treated.120 DEG C of temperature, time 24h.
Table 3
Note：The numbering that 3-1 is expressed as table 3 is 1 flask, and other numberings are similar.
0.2~0.5molL of urea ethanol solution concentration-1In the range of in the case of, it is heat treated after cylinder can be complete
It is whole, and can integral post after drying.
Embodiment 4
Take four round-bottomed flasks, number consecutively 1,2,3,4.With reference to table 4, PEG (10000), absolute ethyl alcohol dress are weighed respectively
In entering round-bottomed flask, it is put into 60 DEG C of water-baths and is all dissolved to PEG, cools down and sequentially add zirconium-n-propylate, ice in backward flask
Acetic acid, the concentrated sulfuric acid, add magneton, be placed on and 20min is stirred on magnetic stirring apparatus, and colloidal sol is distributed into 20 (each round-bottomed flasks
5 pipes can be filled) in the mould of 4cm, be placed on gel in 40 DEG C of water-baths, by gel after wet cylinder be placed in 40 DEG C and 60 DEG C
Water-bath is successively aged 24h.
Table 4
Note：The numbering that 4-1 is expressed as table 4 is 1 flask, and other numberings are similar.
As shown in table 4, zirconium-n-propylate is worked as：Acetic acid：Ethanol mol ratio is 1:3:When 3, can obtain complete, shrinkage factor is small, and
The preferable integral post of mechanical strength.
Although having been presented for some embodiments of the present invention herein, it will be appreciated by those of skill in the art that
Without departing from the spirit of the invention, the embodiments herein can be changed.Above-described embodiment be it is exemplary, no
Should be using the embodiments herein as the restriction of interest field of the present invention.
Claims (2)
1. a kind of preparation method of zirconium oxide integral post, it is characterised in that comprise the following steps：
(1) preparation of wet gel：Weigh appropriate PEG and absolute ethyl alcohol be fitted into round-bottomed flask, be put into water-bath mix to
PEG is all dissolved, and zirconium-n-propylate, glacial acetic acid, the concentrated sulfuric acid are sequentially added in the backward flask of cooling, and the zirconium-n-propylate is dense with described
The mass ratio of sulfuric acid is 1.64/0.16, and the zirconium-n-propylate is 1.64/0.04, the normal propyl alcohol with the mass ratio of the PEG
The mol ratio of zirconium, the glacial acetic acid and the absolute ethyl alcohol is 1:3:3；Magneton is subsequently adding, in stirring on magnetic stirring apparatus
Afterwards, colloidal sol is obtained, the colloidal sol is placed in gel in water-bath, by the wet cylinder water-bath ageing of gained after gel；
(2) urea ethanol solution heat treatment：It is 0.2~0.5mo1L with concentration-1Urea ethanol solution 120 DEG C heat treatment
Wet gel cylinder after the ageing；
(3) integral post is dried：Dry the cylinder after the heat treatment；
(4) Muffle furnace calcination：Dried integral post is taken out, calcination in Muffle furnace is put into.
2. the preparation method of zirconium oxide integral post as claimed in claim 1, it is characterised in that the urea ethanol solution it is dense
It is 0.5mo1L to spend-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510439874.1A CN105056875B (en) | 2015-07-23 | 2015-07-23 | The preparation method of zirconium oxide integral post |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510439874.1A CN105056875B (en) | 2015-07-23 | 2015-07-23 | The preparation method of zirconium oxide integral post |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105056875A CN105056875A (en) | 2015-11-18 |
| CN105056875B true CN105056875B (en) | 2017-06-06 |
Family
ID=54486514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510439874.1A Expired - Fee Related CN105056875B (en) | 2015-07-23 | 2015-07-23 | The preparation method of zirconium oxide integral post |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105056875B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395979A (en) * | 2018-04-25 | 2019-11-01 | 苏州拜博机电科技有限公司 | A kind of direct write forming method of zirconia ceramics |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7547369B2 (en) * | 2006-08-31 | 2009-06-16 | Ferro Corporation | Method of making multilayer structures using tapes on non-densifying substrates |
| CN103771511B (en) * | 2014-02-20 | 2015-04-29 | 安徽工业大学 | Preparation method of anatase titanium dioxide nanocrystalline sol |
-
2015
- 2015-07-23 CN CN201510439874.1A patent/CN105056875B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105056875A (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Epitope imprinted polyethersulfone beads by self-assembly for target protein capture from the plasma proteome | |
| CN104014320B (en) | A kind of aqueous metal organic frame molecular engram material of enriched with trace meta-tolyl-N-methylcarbamate (MTMC) | |
| Mao et al. | Furfural separation from aqueous solution by pervaporation membrane mixed with metal organic framework MIL-53 (Al) synthesized via high efficiency solvent-controlled microwave | |
| CN110643141B (en) | Preparation method of silicon oxide/phenolic aldehyde binary composite aerogel | |
| WO2012100592A1 (en) | Zwitterionic hydrophilic chromatography stationary phase and manufacturing method thereof | |
| CN102225249A (en) | Preparation method of organic-inorganic hybrid monolithic capillary column | |
| CN111072852B (en) | Mesoporous SiO2Preparation method of surface-initiated boron affinity imprinted polymer material and application of surface-initiated boron affinity imprinted polymer material in extraction of shikimic acid | |
| CN105854634A (en) | Ionic liquid/cellulose acetate blended membrane for gas separation | |
| CN105056875B (en) | The preparation method of zirconium oxide integral post | |
| CN106334343B (en) | A kind of preparation method and applications of agar sugar bonding silica-gel hydridization integral post | |
| CN109776460A (en) | A method of Furfural Production from Xylose is catalyzed using solid acid catalyst | |
| CN102872913A (en) | Preparation method of sulfonic acid type polystyrene sphere with catalyzing performance | |
| CN106861446A (en) | A kind of microporous polymer membranes, its preparation method and application | |
| CN103418355A (en) | Sol-gel molecularly-imprinted solid-phase microextraction head and preparation method thereof | |
| CN102872613B (en) | Preparation method of organic-inorganic hybridization monolithic column | |
| CN104650300B (en) | A kind of radome unsaturated polyester resin and preparation method thereof | |
| Lie et al. | Molecularly imprinted mesoporous silica: Potential of the materials, synthesis and application in the active compound separation from natural product | |
| CN107519850B (en) | Preparation of hybrid silica gel monolithic material for chromatographic separation, material and application | |
| CN102626609A (en) | Organic-inorganic hybrid protein molecular engram capillary tube monolithic column | |
| CN109772290A (en) | A kind of preparation method of cerium zirconium sosoloid | |
| CN106115650B (en) | A kind of aluminium dihydrogen tripolyphosphate hollow microsphere and preparation method thereof | |
| Kadoi et al. | Fabrication and characterization of a cellulose monolith-like particle for virus purification | |
| Ji et al. | Separation and purification of horseradish peroxidase from horseradish roots using a novel integrated method | |
| CN105885346B (en) | The organic micro-capsule hybridized film of sulfonated polyether-ether-ketone-amination and preparation and application | |
| CN103627000B (en) | A kind of preparation method of ethyl silicon oil and application |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170606 Termination date: 20200723 |