CN103285836A - Surface imprinting functional adsorbing material and preparation method thereof - Google Patents
Surface imprinting functional adsorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of an adsorbing material, and provides a surface imprinting functional attapulgite adsorbing material. According to the invention, firstly a silane coupling agent is adopted to modify attapulgite, and then template molecules, a functional monomer, a cross-linking agent, an initiator and modified attapulgite powder are uniformly mixed in distilled water and reacted under a nitrogen atmosphere, so as to produce the surface imprinting functional attapulgite adsorbing material. The prepared adsorbing material has good adsorptive property and adsorptive selectivity to the template molecules. The preparation method is simple and environmentally friendly, and the cost is low.
Description
Technical field
The present invention relates to a kind of surface imprinting functionalization sorbing material and preparation method thereof, be specifically related to a kind of preparation method of attapulgite surface molecule print sorbing material.
Background technology
Attapulgite claims palygorskite again, be that a kind of porous type chain stratiform contains Shuifu County's zeopan class clay mineral, its skeleton structure is the 3 D stereo shape, interconnected and form by sharing the summit by silicon-oxy tetrahedron and magnalium octahedron, zeolite cavity and hole run through total, are a kind of porous mineral matters, crystal structure inside has a large amount of zeolite channels, and crystals zeolite cavity size unanimity, make its effect with molecular sieve, can be used for the absorption of various industrial wastewaters.Because the limitation of this body structure of attapulgite makes that the adsorptive selectivity of attapulgite is poor.
Molecular imprinting is on the basis of the existing biology enzyme of simulating nature circle and corresponding substrate, antibody and antigen equimolecular recognition reaction, is template with the target molecule, synthetic experimental technique with high molecular polymer of particular molecule recognition function.The molecular engram process mainly comprised for 3 steps: 1. prepare covalent complex or form non-covalent addition compound product between function monomer and template molecule; 2. this monomer-template complex (or addition product) is carried out polymerization; 3. slough template molecule by means such as extraction, wash-outs.Molecularly imprinted polymer is the core of molecular imprinting, and its special molecule distinguishability makes aspects such as it separates at SPE, film, isomer separation, bionical sensing have a wide range of applications with good stable.
Summary of the invention
Technical problem to be solved by this invention is: in the prior art, because the limitation of this body structure of attapulgite makes that the adsorptive selectivity of attapulgite is poor.
For solving this technical problem, the technical solution used in the present invention is: the invention provides a kind of surface imprinting functionalization attapulgite sorbing material, select for use malachite green or rhodamine B as template molecule, therefore, this sorbing material has excellent adsorptive selectivity to malachite green or rhodamine B molecule.
The present invention also provides a kind of preparation method of above-mentioned surface imprinting functionalization attapulgite sorbing material, and concrete steps are:
(1) attapulgite powder and organic solvent are placed round-bottomed flask with solid-liquid mass ratio 1:15-1:40, ultrasonic processing fully homogenizes, drip silane coupler then, 80-100 ℃ of reaction 12-24h, after reaction finishes, filtration, methanol wash, chloroform washing final vacuum drying, grinding is sieved, namely get silane coupler modified attapulgite
Wherein, organic solvent is toluene or dimethylbenzene, and silane coupler is VTES, vinyltrimethoxy silane or vinyl three (2-methoxy ethoxy) silane, and the mass ratio of silane coupler and attapulgite is 2:1-5:1;
(2) template molecule of 1 times of weight and the function monomer of 5-10 times of weight are dissolved in the distilled water of 300-500 times of weight, after the stirring and dissolving, add the silane coupler modified attapulgite that obtains in the step (1) of 20-60 times of weight, vigorous stirring is fully mixed template molecule, function monomer, modified attapulgite; And then the crosslinking agent of 5 times of weight of adding template molecule and the initator of 0.5-1 times of weight, N
2Under the protection, 30-60 ℃ of reaction 2-6h is after reaction finishes; as eluant, eluent, soxhlet extraction method flush away template molecule is after fully washing with distilled water again with the mixture of methyl alcohol and acetic acid; vacuum drying, grinding are sieved, and namely get surface imprinting functionalization attapulgite sorbing material
Template molecule is selected from malachite green or rhodamine B, function monomer is acrylamide or Methacrylamide, crosslinking agent is N ' N-methylene-bisacrylamide or piperazine diacrylamine, initator is selected from ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate, in the mixture of methyl alcohol and acetic acid, the volume ratio of methyl alcohol and acetic acid is 9:1.
The invention has the beneficial effects as follows: the surface imprinting functionalization sorbing material of the present invention's preparation, adopt surface imprinted technology, molecularly imprinted polymer is coated on the modified attapulgite surface, has improved the absorption property of attapulgite and to the adsorptive selectivity of template molecule; And the preparation method is simple, environmental protection, and is with low cost.
Description of drawings
Fig. 1 is the surface imprinting functionalization attapulgite of preparation in embodiment 1, Comparative Examples 1, embodiment 3, the Comparative Examples 3, and former attapulgite, to the absorption property of single target contaminant malachite green.
Fig. 2 is the surface imprinting functionalization attapulgite of preparation in embodiment 1, Comparative Examples 1, embodiment 3, the Comparative Examples 3, and former attapulgite, under coexistence chaff interference methylene blue existence condition, to the absorption property of target contaminant malachite green.
The specific embodiment
Embodiment 1
(1) 200 purpose attapulgite powders and toluene are placed round-bottomed flask with solid-liquid mass ratio 1:15, ultrasonic processing 60min fully homogenizes, and drips VTES then, and the mass ratio of itself and attapulgite is 2:1,80 ℃ of reaction 24h; After reaction finishes, filtration, methanol wash, chloroform washing final vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite;
(2) 1g malachite green and 5g acrylamide are dissolved in the 300mL distilled water, after the stirring and dissolving, add the silane coupler modified attapulgite that obtains in the 20g step (1), vigorous stirring 30min fully mixes template molecule, function monomer, modified attapulgite; And then adding 5g crosslinking agent N ' N-methylene-bisacrylamide and 0.5g initiator ammonium persulfate, N
2Under the protection, 30 ℃ of reaction 6h, reaction is used V after finishing
Methyl alcohol: V
Acetic acid=9:1 is eluant, eluent, soxhlet extraction method flush away template molecule, and after fully washing with distilled water, vacuum drying, grinding are sieved, and namely get the surface imprinted malachite green sorbing material of attapulgite (ATP-MIPs-I) again.
Comparative Examples 1
All the other preparation processes are all identical with embodiment 1, just no longer add the template molecule malachite green in the step (2), finally obtain non-imprinted polymer attapulgite sorbing material (ATP-NIPs-I).
Embodiment 2
(1) 200 purpose attapulgite powders and dimethylbenzene are placed round-bottomed flask with solid-liquid mass ratio 1:40, ultrasonic processing 60min fully homogenizes, and drips vinyltrimethoxy silane then, the mass ratio 5:1 of itself and attapulgite, 100 ℃ of reaction 12h; After reaction finishes, filtration, methanol wash, chloroform washing final vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite;
(2) 1g rhodamine B and 10g Methacrylamide are dissolved in the 500mL distilled water, after the stirring and dissolving, add the silane coupler modified attapulgite that obtains in the 60g step (1), vigorous stirring 60min fully mixes template molecule, function monomer, modified attapulgite; And then adding 5g crosslinking agent piperazine diacrylamine and 1g initator sodium peroxydisulfate, N
2Under the protection, 60 ℃ of reaction 2h, reaction is used V after finishing
Methyl alcohol: V
Acetic acid=9:1 is eluant, eluent, soxhlet extraction method flush away template molecule, and after fully washing with distilled water, vacuum drying, grinding are sieved, and namely get surface imprinting functionalization attapulgite sorbing material (ATP-MIPs-II) again.
Comparative Examples 2
All the other preparation processes are all identical with embodiment 2, just no longer add the template molecule rhodamine B in the step (2), finally obtain non-imprinted polymer attapulgite sorbing material (ATP-NIPs-II).
Embodiment 3
(1) 200 purpose attapulgite powders and toluene are placed round-bottomed flask with solid-liquid mass ratio 1:25, ultrasonic processing 60min fully homogenizes, and drips vinyl three (2-methoxy ethoxy) silane then, the mass ratio of itself and attapulgite is 3:1,90 ℃ of reaction 18h; After reaction finishes, filtration, methanol wash, chloroform washing final vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite;
(2) 1g malachite green and 8g acrylamide are dissolved in the 400mL distilled water, after the stirring and dissolving, add the silane coupler modified attapulgite that obtains in the 30g step (1), vigorous stirring 45min fully mixes template molecule, function monomer, modified attapulgite; And then adding 5g crosslinking agent N ' N-methylene-bisacrylamide and 0.8g initiator potassium persulfate, N
2Under the protection, 45 ℃ of reaction 4h, reaction is used V after finishing
Methyl alcohol: V
Acetic acid=9:1 is eluant, eluent, soxhlet extraction method flush away template molecule, and after fully washing with distilled water, vacuum drying, grinding are sieved, and namely get the surface imprinted malachite green sorbing material of attapulgite (ATP-MIPs-III) again.
Comparative example 3
All the other preparation processes are all identical with embodiment 3, just no longer add the template molecule malachite green in the step (2), finally obtain non-imprinted polymer attapulgite sorbing material (ATP-NIPs-III).
Embodiment 4
(1) 200 purpose attapulgite powders and dimethylbenzene are placed round-bottomed flask with solid-liquid mass ratio 1:30, ultrasonic processing 60min fully homogenizes, and drips vinyl three (2-methoxy ethoxy) silane then, the mass ratio 4:1 of itself and attapulgite, 85 ℃ of reaction 24h; After reaction finishes, filtration, methanol wash, chloroform washing final vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite;
(2) 1g rhodamine B and 6g Methacrylamide are dissolved in the 300mL distilled water, after the stirring and dissolving, add the silane coupler modified attapulgite that obtains in the 40g step (1), vigorous stirring 60min fully mixes template molecule, function monomer, modified attapulgite; And then adding 5g crosslinking agent piperazine diacrylamine and 0.6g initiator ammonium persulfate, N
2Under the protection, 50 ℃ of reaction 5h, reaction is used V after finishing
Methyl alcohol: V
Acetic acid=9:1 is eluant, eluent, soxhlet extraction method flush away template molecule, and after fully washing with distilled water, vacuum drying, grinding are sieved, and namely get surface imprinting functionalization attapulgite sorbing material (ATP-MIPs-IV) again.
Comparative example 4
All the other preparation processes are all identical with embodiment 4, just no longer add the template molecule rhodamine B in the step (2), finally obtain non-imprinted polymer attapulgite sorbing material (ATP-NIPs-IV).
Adsorption experiment:
Take by weighing the 100mg adsorbent, in the dye solution of adding 100mL50mg/L (the dyestuff solute is respectively malachite green, rhodamine B, methylene blue), adsorb 4h under the room temperature, filter, measure the dye strength in the filtrate.Variation according to dye strength before and after the absorption is calculated as follows the dyestuff clearance:
In the formula: C
0Dye strength (mgL before the-absorption
-1); C
eDye strength (mgL after the-adsorption equilibrium
-1).
With embodiment 1～4, in the comparative example 1～4, the gained sample carries out above-mentioned adsorption experiment respectively, and the result is as shown in table 1.
The absorption property of the various samples of table 1
Can find out from last table, compare with former attapulgite, no matter be that molecularly imprinted polymer coats attapulgite or non-molecularly imprinted polymer coats attapulgite, they all increase to the absorption property of malachite green, rhodamine B, methylene blue homogencous dyes solution.
In addition, as can be seen from Figure 1, ATP-MIPs-I, ATP-NIPs-I, ATP-MIPs-III, ATP-NIPs-III to the absorption property of malachite green apparently higher than attapulgite.
We select for use malachite green as target contaminant, serve as the coexistence chaff interference with the methylene blue of same concentrations, investigate the adsorptive selectivity of ATP-MIPs-I, ATP-NIPs-I, ATP-MIPs-III, ATP-NIPs-III.
As seen from Figure 2: in reaction system, after adding coexistence chaff interference methylene blue, surface imprinting functionalization attapulgite sorbing material (ATP-MIPs-I, ATP-MIPs-III) is constant substantially to the clearance of target contaminant malachite green, but because the interference of coexistence pollutant methylene blue is arranged, attapulgite, non-molecularly imprinted polymer coating attapulgite (ATP-NIPs-I, ATP-NIPs-III) obviously reduce the clearance of target contaminant malachite green, and this shows after attapulgite is through the surface molecule print functionalization to have the special molecular recognition function.
Claims (9)
1. surface imprinting functionalization sorbing material, it is characterized in that: described sorbing material is surface imprinting functionalization attapulgite sorbing material, selects for use malachite green or rhodamine B as template molecule.
2. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 1 is characterized in that: described method concrete steps are,
(1) attapulgite powder and organic solvent are placed round-bottomed flask with solid-liquid mass ratio 1:15-1:40, ultrasonic processing fully homogenizes, drip silane coupler then, 80-100 ℃ of reaction 12-24h, after reaction finishes, filtration, methanol wash, chloroform washing final vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite;
(2) template molecule of 1 times of weight and the function monomer of 5-10 times of weight are dissolved in the distilled water of 300-500 times of weight, after the stirring and dissolving, add the silane coupler modified attapulgite that obtains in the step (1) of 20-60 times of weight, vigorous stirring is fully mixed template molecule, function monomer, modified attapulgite; And then the crosslinking agent of 5 times of weight of adding template molecule and the initator of 0.5-1 times of weight, N
2Under the protection, 30-60 ℃ of reaction 2-6h is after reaction finishes; as eluant, eluent, soxhlet extraction method flush away template molecule is after fully washing with distilled water again with the mixture of methyl alcohol and acetic acid; vacuum drying, grinding are sieved, and namely get surface imprinting functionalization attapulgite sorbing material.
3. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: the organic solvent described in the step (1) is selected from toluene or dimethylbenzene.
4. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: the silane coupler described in the step (1) is selected from, VTES, vinyltrimethoxy silane or vinyl three (2-methoxy ethoxy) silane, the mass ratio of silane coupler and attapulgite is 2:1-5:1.
5. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: the template molecule described in the step (2) is selected from malachite green or rhodamine B.
6. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: the function monomer described in the step (2) is selected from acrylamide or Methacrylamide.
7. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: the crosslinking agent described in the step (2) is selected from N ' N-methylene-bisacrylamide or piperazine diacrylamine.
8. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: the initator described in the step (2) is selected from ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
9. the preparation method of surface imprinting functionalization sorbing material as claimed in claim 2, it is characterized in that: in the mixture of the methyl alcohol described in the step (2) and acetic acid, the volume ratio of methyl alcohol and acetic acid is 9:1.
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| CN103613720A (en) * | 2013-11-20 | 2014-03-05 | 东南大学 | Method for preparing silane coupling agent modified attapulgite surface molecular imprinting material aiming at bisphenol A |
| CN103623788A (en) * | 2013-11-22 | 2014-03-12 | 江苏大学 | Preparation method of magnetic mesoporous free radical controlled polymer ion printing adsorbing agent |
| CN105381791A (en) * | 2015-11-20 | 2016-03-09 | 淮阴师范学院 | Preparation method of attapulgite-based molecular imprinting type CO2 adsorbing material |
| CN106179507A (en) * | 2016-06-30 | 2016-12-07 | 常州大学 | A kind of molecularly imprinted polymer modifies the preparation method of nano ZnO photocatalyst |
| CN107185419A (en) * | 2017-07-04 | 2017-09-22 | 合肥市大卓电力有限责任公司 | A kind of air purifier dedusting film and preparation method |
| CN113461539A (en) * | 2021-08-02 | 2021-10-01 | 江苏扬农化工集团有限公司 | Method for preparing organic diamine from amino nitrile organic matter |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613720A (en) * | 2013-11-20 | 2014-03-05 | 东南大学 | Method for preparing silane coupling agent modified attapulgite surface molecular imprinting material aiming at bisphenol A |
| CN103623788A (en) * | 2013-11-22 | 2014-03-12 | 江苏大学 | Preparation method of magnetic mesoporous free radical controlled polymer ion printing adsorbing agent |
| CN103623788B (en) * | 2013-11-22 | 2016-04-06 | 江苏大学 | A kind of preparation method of magnetic mesoporous free radical controllable polymerization ion blotting adsorbent |
| CN105381791A (en) * | 2015-11-20 | 2016-03-09 | 淮阴师范学院 | Preparation method of attapulgite-based molecular imprinting type CO2 adsorbing material |
| CN106179507A (en) * | 2016-06-30 | 2016-12-07 | 常州大学 | A kind of molecularly imprinted polymer modifies the preparation method of nano ZnO photocatalyst |
| CN107185419A (en) * | 2017-07-04 | 2017-09-22 | 合肥市大卓电力有限责任公司 | A kind of air purifier dedusting film and preparation method |
| CN113461539A (en) * | 2021-08-02 | 2021-10-01 | 江苏扬农化工集团有限公司 | Method for preparing organic diamine from amino nitrile organic matter |
| CN113461539B (en) * | 2021-08-02 | 2023-11-21 | 江苏扬农化工集团有限公司 | Method for preparing organic diamine from amino nitrile organic matter |
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