CN106732439A - A kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent - Google Patents
A kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent Download PDFInfo
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- CN106732439A CN106732439A CN201510813835.3A CN201510813835A CN106732439A CN 106732439 A CN106732439 A CN 106732439A CN 201510813835 A CN201510813835 A CN 201510813835A CN 106732439 A CN106732439 A CN 106732439A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention discloses a kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent, including the technique such as the polymerization of polymeric precursor, hybridisation silica gel emulsion, molecular engram microsphere and area load, template molecule desorption.The present invention is with Sudan red 1 as representative, loaded by the preparation of dispersed molecular engram microsphere and its effective bonding on silica-gel carrier surface, it is prepared for the adsorbent of molecular engram polymerizing microballoons-silica-gel carrier area load, prepared adsorbent surface dispersed polymer particles of the bonding with higher volumes capacity, traditional molecular engram bulk polymer is avoided because template molecule is embedded deeply, the deficiency of long action time, it also avoid molecular imprinted polymer on surface causes the small limitation of template molecule capacity because polymer layer is very thin, adsorbent speed of action and adsorption capacity can be significantly improved, can be applied to the efficient absorption of the test substances such as Sudan red 1.
Description
Technical field
The invention belongs to analytical chemistry field, and in particular to a kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent.
Background technology
Molecular imprinting technology（Molecuar imprinting
technolory）It is new function macromolecule technology of preparing developed in recent years, is a cross discipline of the subjects such as polymer chemistry, material science, environmental science.According to template molecule and the difference of the mode of action of function monomer, molecular imprinting technology is broadly divided into covalent, non-covalent and half covalent blotting, classifies according to polymerization, is segmented into mass polymerization, surface molecule print method and suspension polymerization etc..
Mass polymerization is to prepare MIPs most conventional methods, and template molecule and function monomer are sufficiently mixed in appropriate solvent, adds crosslinking agent and initiator, cross-linked polymeric to obtain hard block polymer；Again by polymer crushing, grinding, sieving, and with the particle of appropriate particle size is obtained after acetone sedimentation, finally elute and remove template molecule, it is standby after drying.This method is simple to operate, with low cost, easy to spread, weak point is to need in polymerization process by the tedious steps such as smashing, grinding and sieve to pieces, waste time and energy, and space structure and the identification hole of polymer can be destroyed, weaken specific adsorption effect of the polymer to template molecule；Simultaneously template molecule can be caused to embed using the crosslinking agent of high concentration too deep, wash-out difficulty is high, solvent consumption is big.Surface molecule print method is to improve the combination speed of recognition site and template molecule on the surface of imprinted polymer by the way that Molecular Recognization site is set up, the method for strengthening imprinted polymer adsorption efficiency.Surface imprinted work fast, but loaded on Nano microsphere surface, actuating quantity is small, is unfavorable for complex sample efficiently concentrating.Suspension polymerization is the reliable method for preparing molecular engram microsphere.Monomer, pore-foaming agent and dispersant are generally constituted into uniform mixed solution, polymerization is triggered to produce insoluble polymer microballoon under agitation, need not move through the tediously long processes such as broken, grinding, the trace microballoon of regular shape can be obtained by the ratio for adjusting dispersant, chromatograph packing material is suitable as.
At present, in terms of molecular engram polymeric material, document report is concentrated mainly on the polymerisation in bulk of the monomers such as methacrylic acid or 4-vinylpridine, suspension polymerisation, surface imprinted, existing molecularly imprinted polymer focuses primarily upon the exploration and research of polymerisation, Depth Study is not carried out in terms of the assembling of polymerizing microballoons and the research of load pattern, there is conventional bulk polymerization, the template molecule of precipitation polymerization embeds deep, long action time；Surface imprinted work fast, Nano microsphere area load capacity is small, is unfavorable for the deficiencies such as complex sample efficiently concentrating.Therefore, the present invention is with common Sudan red 1 as template molecule, load isotype and design by introducing suspension polymerisation and surface bond, innovate the dispersed trace microballoon and Silica Surface bonding load technology research carried out, the new efficient SPE sorbing material with selection recognition capability of development, has great importance to setting up tonyred equimolecular print identification technology.
The content of the invention
It is an object of the invention to provide a kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent, the adsorbent of molecular engram polymerizing microballoons-silica-gel carrier area load is prepared, significantly improve adsorbent speed of action and adsorption capacity.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent, it is characterised in that as steps described below：
Siloxanyl monomers mixed liquor is mixed and is uniformly dispersed by step A, polymeric precursor under the conditions of 0 DEG C of low temperature and logical nitrogen, obtains sol-gel polymerization presoma；
Step B, hybridisation silica gel emulsion, with synthetic dyestuffs as template molecule, template molecule solution is mixed with above-mentioned polymeric precursor, is stirred at room temperature well mixed, obtains the sol-gel polymerization emulsion with synthetic dyestuffs as template molecule；
Step C, molecular engram microsphere is polymerized and area load, to grind during silica obtained particle after sieving adds the sol-gel polymerization emulsion obtained by step B, stirred and evenly mixed at 20 DEG C, add the acetic acid solution of 1.0 mol/L, 20 DEG C of h of water-bath 24, naturally cool to room temperature, obtain the molecular engram polymer particles-silica gel supported adsorbent containing dye molecule template；
Step D, template molecule desorption cleans molecular engram polymer particles-silica gel supported adsorbent described above using methyl alcohol, acetone successively, is placed in aging 10 h in 100 DEG C of drying boxes；Continuation volume ratio is 9：1 methanol-acetic acid mixed liquor carries out wash-out 48h by apparatus,Soxhlet's to described load type adsorbing agent thing, and neutrality is washed till with methyl alcohol, and 80 DEG C of vacuum drying 12h obtain the molecular engram polymer particles-silica gel supported adsorbent to dye molecule with Specific adsorption.
Siloxanyl monomers mixed liquor described in step A is 3- aminopropyl triethoxysilanes and tetraethoxy silica alkane mixed liquor, and both volume ratios are 1：1；Synthetic dyestuffs template molecule described in step B is Sudan red 1 molecule, and described sol-gel polymerization presoma and the volume ratio of template molecule solution are 12：100；Acetic acid solution and the volume ratio of sol-gel polymerization emulsion described in step C are 3：100.
After using such scheme, remarkable advantage of the invention is：Integrated application of the present invention microsphere surface aggregate and sol-gel polymerizations two kinds of advantages of technology, silicone hydroxyl condensation reaction based on silica-gel carrier surface, condensation reaction is produced by the silicone hydroxyl and the silica group in sol-gel polymerization particle on silica-gel carrier surface, siloxane sol-gel polymer particle is promoted to produce chemical bonding with silica-gel carrier surface, the polymer particles dispersion layer of the similar surfaces imprinted polymer of stabilization is formed in silica-gel carrier surface aggregate, by polymerization parameter control, polymer particles size can effectively be controlled in micro-nano rank, avoid in mass polymerization causes Molecular Recognization speed slow because polymer molecular template embedding is deep, the low bottleneck problem of efficiency, realize microsphere quick identification and desorption in polymer particle；On the other hand, the present invention passes through sol-gel polymerization technology application, so that polymeric precursor forms monodisperse particle in silica-gel carrier surface aggregate, form the polymer particles dispersion layer of stabilization, polymer particle capacity is big, it is to avoid surface imprinted polymerization because polymer layer is very thin causes the small deficiency of microsphere capacity.
It is deep that the present invention not only overcomes traditional imprinted material polymerization technique template molecule embedding, action time tediously long technical deficiency, while also eliminating the common molecular imprinting surface polymer problem that polymer layer is thin after completion of the polymerization reaction, microsphere capacity is small, sorption efficiency is low.By taking Sudan red 1 as an example, disclosed technical method preparation condition is simple, gained polymeric material stabilization for the present invention, and specific adsorption efficiency is higher, can be applied to effective extraction of the materials such as tonyred.
Brief description of the drawings
Fig. 1 is Sudan red I molecular imprinted polymeric（MIPs）；
Fig. 2 is non-molecularly imprinted polymer（a：NIPs）, activated silica gel（b）With Sudan molecules imprinted polymer（c：MIPs）Curve of adsorption kinetics；
Fig. 3 is Sudan molecules imprinted polymer（MIPs）, non-molecularly imprinted polymer and activated silica gel elution kinetics profile.
Specific embodiment
（1）The preparation of molecular engram material
Activated silica gel：The silica gel for weighing 8.0 g is placed in the round-bottomed flask of 250 mL, adds the Loprazolam aqueous solution of 60 mL 35%.Oil bath heating is refluxed 8 h to 120 DEG C, filtering, is cleaned to neutrality with secondary water repeatedly, and 20 h are dried in 70 DEG C of vacuum drying chambers, is placed in standby in glass desicator.
The synthesis of molecularly imprinted polymer：Pipette 30 mL 5 × 10-3 Tonyred-the acetonitrile solution of mol/L is in 100 mL flasks.Solid mechanical agitating device, adjustment rotating speed is 160-180 rpm, and bath temperature is 20.0 DEG C.Sequentially add 1.8 mL 3- aminopropyl triethoxysilanes（APTES）, in the middle of 0.030 g activated silica gels and 1.8mL tetraethoxysilanes to solution, stir and evenly mix.The acetum of the mol/L of 1.0 mL 1.0 is added dropwise over, is sufficiently stirred for, the h of water-bath 24 at 20 DEG C.Filtering, after being cleaned with ethanol, is placed in aging 10 h in 100 DEG C of drying boxes.
The wash-out of molecular engram template：The polymer of above-mentioned preparation is carried out into soxhlet's extraction with the methanol-acetic acid mixed liquor that volume ratio is 9 to 1, until Sudan red 1 extraction is clean.Again with methanol is washed till neutrality, and 80 DEG C of 12 h of vacuum drying obtain Sudan red 1 molecular imprinted polymer on surface（Fig. 1）.
（2）Performance characterization
Adsorption dynamics adsorption kinetics：The activated silica gel and Sudan red I molecular imprinted polymeric of 0.050 g are weighed respectively in container, the Sudan red 1 solution of the μ g/mL of 5.0 mL 0.5 is added, vibration is mixed, and the absorbance of ultraviolet detection solution, obtains non-molecularly imprinted polymer at regular intervals（a：NIPs）, activated silica gel（b）With Sudan molecules imprinted polymer（c：MIPs）, curve of adsorption kinetics（Fig. 2）.
Elution kinetics：MIPs, NIPs and activated silica gel of 0.050 g are weighed respectively in the middle of three conical flasks, respectively toward Sudan red 1-methanol/water solution that 10.0 μ g/mL are added in each conical flask（1:9, v/v）.Vibrate 1.5 h, filtering, clean uniform to powder color with a small amount of secondary water, powder is collected in the middle of 5 mL test tubes, 5.0 mL methyl alcohol are added to vibrate, the concentration of wash-out solution is detected with HPLC-DAD at regular intervals, MIPs, NIPs adsorption capacity of different time points is calculated, Sudan molecules imprinted polymer is obtained（MIPs）, non-molecularly imprinted polymer and activated silica gel elution kinetics profile（Fig. 3）.
The method of the present invention includes polymeric precursor, hybridisation silica gel emulsion, molecular engram microsphere polymerization and area load, template molecule desorption.Cause long action time because template molecule is embedded deeply for common molecular engram bulk polymer, molecular imprinted polymer on surface causes the small problem of template molecule capacity because polymer layer is very thin, the present invention is loaded by the sol-gel polymerizations of dispersed molecular engram microsphere and its bonding on silica-gel carrier surface, by taking Sudan red 1 as an example, the adsorbent of molecular engram polymerizing microballoons-silica-gel carrier area load is prepared, adsorbent speed of action and adsorption capacity is significantly improved.
Presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification are the foregoing is only, should all belong to covering scope of the invention.
Claims (2)
1. a kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent, it is characterised in that as steps described below：
Siloxanyl monomers mixed liquor is mixed and is uniformly dispersed by step A, polymeric precursor under the conditions of 0 DEG C of low temperature and logical nitrogen, obtains sol-gel polymerization presoma；
Step B, hybridisation silica gel emulsion, with synthetic dyestuffs as template molecule, template molecule solution is mixed with above-mentioned polymeric precursor, is stirred at room temperature well mixed, obtains the sol-gel polymerization emulsion with synthetic dyestuffs as template molecule；
Step C, molecular engram microsphere is polymerized and area load, to grind during silica obtained particle after sieving adds the sol-gel polymerization emulsion obtained by step B, stirred and evenly mixed at 20 DEG C, add the acetic acid solution of 1.0 mol/L, 20 DEG C of h of water-bath 24, naturally cool to room temperature, obtain the molecular engram polymer particles-silica gel supported adsorbent containing dye molecule template；
Step D, template molecule desorption cleans molecular engram polymer particles-silica gel supported adsorbent described above using methyl alcohol, acetone successively, is placed in aging 10 h in 100 DEG C of drying boxes；Continuation volume ratio is 9：1 methanol-acetic acid mixed liquor carries out wash-out 48h by apparatus,Soxhlet's to described load type adsorbing agent thing, and neutrality is washed till with methyl alcohol, and 80 DEG C of vacuum drying 12h obtain the molecular engram polymer particles-silica gel supported adsorbent to dye molecule with Specific adsorption.
2. a kind of preparation method of molecular engram polymer particles-silica gel supported adsorbent as claimed in claim 1, it is characterised in that：Siloxanyl monomers mixed liquor described in step A is 3- aminopropyl triethoxysilanes and tetraethoxy silica alkane mixed liquor, and both volume ratios are 1：1；Synthetic dyestuffs template molecule described in step B is Sudan red 1 molecule, and described sol-gel polymerization presoma and the volume ratio of template molecule solution are 12：100；Acetic acid solution and the volume ratio of sol-gel polymerization emulsion described in step C are 3：100.
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Cited By (1)
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|---|---|---|---|---|
| CN113201137A (en) * | 2021-04-25 | 2021-08-03 | 中国石油大学(北京) | Daidzein sol-gel surface molecularly imprinted polymer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055831A (en) * | 2011-10-20 | 2013-04-24 | 中国科学院兰州化学物理研究所 | Preparation method of inorganic core-shell type quercetin molecularly imprinted polymer microsphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055831A (en) * | 2011-10-20 | 2013-04-24 | 中国科学院兰州化学物理研究所 | Preparation method of inorganic core-shell type quercetin molecularly imprinted polymer microsphere |
Non-Patent Citations (1)
| Title |
|---|
| SHUO WANG等: "Synthesis and Characterization of a Molecularly Imprinted Silica Gel Sorbent for the On-Line Determination of Trace Sudan I in Chilli Powder through High-Performance Liquid Chromatography", 《J. AGRIC. FOOD CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201137A (en) * | 2021-04-25 | 2021-08-03 | 中国石油大学(北京) | Daidzein sol-gel surface molecularly imprinted polymer and preparation method thereof |
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