CN104258826A - Active/controllable mesoporous material ion-surface imprinted polymer as well as preparation method and application of ion-surface imprinted polymer - Google Patents
Active/controllable mesoporous material ion-surface imprinted polymer as well as preparation method and application of ion-surface imprinted polymer Download PDFInfo
- Publication number
- CN104258826A CN104258826A CN201410467787.2A CN201410467787A CN104258826A CN 104258826 A CN104258826 A CN 104258826A CN 201410467787 A CN201410467787 A CN 201410467787A CN 104258826 A CN104258826 A CN 104258826A
- Authority
- CN
- China
- Prior art keywords
- mesoporous material
- ion
- imprinted polymer
- preparation
- sba
- 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.)
- Granted
Links
Classifications
-
- 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
- B01J20/22—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides an active/controllable mesoporous material ion-surface imprinted polymer as well as a preparation method and application of the active/controllable mesoporous material ion-surface imprinted polymer, belonging to the technical field of material preparation and separation. The preparation method comprises the following steps of firstly preparing an amino functional mesoporous material, then preparing a mesoporous material grafted with a chain transfer agent, and reacting the mesoporous material grafted with the chain transfer agent with template ions, functional monomers, a cross-linking agent and an initiator, so as to obtain the mesoporous material ion-surface imprinted polymer. According to preparation method, the problems that the thickness of a surface polymer layer is uncontrollable, template molecules cannot be eluted due to great embedding depth, and the adsorption velocity is low are solved; the active/controllable mesoporous material ion-surface imprinted polymer is mainly used for adsorbing corresponding metal ions in a water solution and has excellent adsorption effect and high adsorption capacity at room temperature, and non-specific adsorption is effectively reduced.
Description
Technical field
The invention belongs to environment functional material technical applications, especially a kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method thereof and application.
Background technology
Along with the development of China's nuclear industry, the discharge capacity of middle low-activity waste water constantly increases.Wherein, middle low-activity metallic element is then the important component part of middle low-activity waste water.Harm due to middle radioactive metal ion has stronger disguise, is not easily discovered and the method that its harmfulness not easily passs through chemistry, physics or biology is eliminated, therefore realize its effectively process seem particularly important.The problems such as traditional processing method (as evaporation concentration method, chemical precipitation method and ion-exchange) exists that efficiency is low usually, complex operation and selectivity difference.Therefore, low-activity metal pollutant transaction module in effective exclusive type is set up significant.
Molecular imprinting is a kind of technology being used for preparing the imprinted polymer (MIPs) a certain specific template molecule to singleness identity.The object that will be separated and crosslinking agent carry out copolymerization and prepare granule medium in polymer monomer solution, and then wash-out goes out the object be embedded in medium, just obtains molecularly imprinted polymer object to singleness identity.When object is metal ion, then can be referred to as ion imprinted polymer (IIPs).Surface ion engram technology is the immunoblot method imprinted layer with recognition site being combined in stromal surface.It can overcome that imprinted cavity in traditional blotting techniques embedded deeply effectively, template ion wash-out difficulty and the shortcoming such as mass transfer velocity is slow, thus reaches the object improving imprinted polymer adsorption efficiency.Mesoporous material SBA-15 is widely used as the host material of surface imprinted process because of its homogeneous aperture, large specific area, larger pore volume and good finishing characteristic.
In surface imprinted polymerization field, in order to overcome the defect (as uncontrollable in polymer architecture, template binding site heterogeneity) that conventional free radical polymerization exists, Controlled/Living Radical Polymerization (CRP) is introduced the preparation process of surface imprinted polymer gradually.Wherein, reversible addion-fragmentation chain transfer (RAFT) is polymerized, and as the typical CRP polymerization of one, is introduced the preparation process of molecular imprinted polymer on surface gradually in recent years.But as far as we know, report related to this nearly all concentrates in the preparation of MIP, and few to the concern of IIP.
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of is host material with mesoporous SBA-15, adopts reversible addion-fragmentation chain transfer (RAFT) polymerization preparation to have the metal ion imprinted polymer of controlled architecture.。
The present invention realizes above-mentioned technical purpose by following technological means.
A preparation method for activity/controlled mesoporous material surface ion imprinted polymer, comprises the steps:
I, mesoporous material SBA-15 is carried out purifying and activation;
II, the preparation of amino functional mesoporous material: above-mentioned SBA-15 and silane coupler are refluxed in toluene under oxygen free condition, product is through washing, drying;
III, the preparation of the mesoporous material of grafted chain transfer agent: above-mentioned amino functional mesoporous material is added in the acetonitrile solution 1 of chain-transferring agent, ultrasonic rear ice bath leaves standstill, and adds N, the acetonitrile solution 2 of N-dicyclohexylcarbodiimide, react under room temperature, product is through washing, drying;
IV, the preparation of ion imprinted polymer: the mesoporous material of template ion, function monomer, crosslinking agent, above-mentioned grafted chain transfer agent is stirred in methyl alcohol and acetonitrile mixture, add initator, in water-bath under oxygen free condition, also detect to metal ion washes clean with EDTA solution washing, dry product.
In such scheme, described SBA-15 purifying and activation method are: SBA-15 is left standstill aging 12 ~ 48 h at 80 DEG C, and spend deionized water, 18 ~ 72 h that reflux in ethanol obtain the SBA-15 of purifying; Being placed on concentration is 24 h that reflux in 1.0 ~ 3.0 mol/L hydrochloric acid solutions, is washed till neutral rear dry.
In such scheme, silane coupler described in step II is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane;
Described toluene consumption is that every 6.25 ~ 18.75 g SBA-15 are scattered in 1 L toluene, and described silane coupled agent concentration is 0.05 ~ 0.15 mol/L;
Described return time is 10 ~ 20 h.
In such scheme, in such scheme, chain-transferring agent described in step III is 2-(dodecyl trithiocarbonic acid ester group)-2 Methylpropionic acid (TTCA);
Described acetonitrile content is that every 5.0 ~ 10.0 g amino functional mesoporous materials are placed in 1 L acetonitrile solution, and the concentration of described chain-transferring agent is 0.01 ~ 0.03 mol/L, and described N, N-dicyclohexylcarbodiimide concentration in acetonitrile 2 is 0.04 ~ 0.08 mol/L;
The described reaction time is 10 ~ 20 h.
In such scheme, template ion described in step IV is for being provided by soluble metallic salt, and described function monomer is methacrylic acid, and described crosslinking agent is ethylene glycol dimethacrylate or N, N '-methylene-bisacrylamide, described initator is azodiisobutyronitrile;
In described mixed liquor, the volume ratio of methyl alcohol and acetonitrile is 4:1, described template ion concentration is 5.0 ~ 15.0 mmol/L, the concentration of described function monomer and crosslinking agent is respectively 20.0 ~ 60.0 mmol/L and 50.0 ~ 150.0 mmol/L, described initiator amount is that the mesoporous material of every 50 ~ 100 mg grafted chain transfer agents adds 4 ~ 8 mg initators, and the concentration of described EDTA solution is 0.1 mol/L;
Described bath temperature is 55 ~ 65 DEG C, and the water-bath time is 6 ~ 24 h.
In such scheme, described template ion at least comprises nickel, iron, caesium, copper, strontium, mercury, cobalt, cadmium, manganese, zinc.
In such scheme, described method prepares activity/controlled mesoporous material surface ion imprinted polymer.
Further, described activity/controlled mesoporous material surface ion imprinted polymer is used for corresponding ion in adsorption aqueous solution.
Obtained metal ion trace adsorbent is carried out Dynamic Adsorption and static selective absorption is tested, carries out as follows:
Dynamic Adsorption is tested: ion imprinted polymer is loaded Dynamic Adsorption post, pass into deionized water 10 min, metal ion solution (pH is consistent with deionized water) is passed into adsorption column, and control loading flow velocity with peristaltic pump, the temperature of metal ion solution is controlled by extraneous recirculated water, finally connect efflux with 10 mL color-comparison tubes respectively in different time sections, use Atomic Absorption Spectrometry concentration of metal ions.
Static selective absorption experiment: the mixed liquor of preparation many kinds of metal ions and object ion, the concentration of often kind of ion is consistent, get the solution of the above-mentioned preparation of 25 mL in colorimetric cylinder, add ion imprinted polymer, test fluid is placed in 25 DEG C of water-baths and leaves standstill 12 h, centrifugation obtains supernatant, measures each concentration of metal ions with atomic absorption spectrum and plasma emission spectrometer.
Tool of the present invention has the following advantages:
(1) host material is made with SBA-15, metal ion imprinted polymer is prepared at host surface, avoid the problems such as the template ion wash-out difficulty of traditional trace polymerization existence, and the trace adsorbent obtained has the advantages such as specific area is large, mechanical strength is high, recognition site is survivable, greatly improves the adsorption capacity of imprinted polymer and effectively reduces non-specific adsorption;
(2) achieve the successful grafting of RAFT reagent on SBA-15 surface by simple rear Graft Method, thus RAFT free radical activity controllable polymerization is incorporated in surface imprinted process, synthesize the cesium ion imprinted polymer with controllable appearance;
(3) the metal ion imprinted polymer utilizing the present invention to obtain has higher adsorption capacity, has Adsorption Kinetics and the specific recognition ability to special metal ion fast.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 and amplifies transmission electron microscope picture, and Fig. 1 (a) and Fig. 1 (c) is the scanning electron microscope (SEM) photograph of SBA-15 and Cs (I) ion blotting adsorbent respectively; Fig. 1 (b) and Fig. 1 (d) is the amplification transmission electron microscope picture of SBA-15 and Cs (I) ion blotting adsorbent surface respectively.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1:
(1) mesoporous material SBA-15 is carried out purifying and activation: take 2 mg SBA-15 and leave standstill aging 12 h under 80 ° of C, then fully wash by deionized water, 18 h that finally reflux in ethanol remove the SBA-15 that residual template obtains purifying; SBA-15 after purifying is placed in 1.0 mol/L hydrochloric acid solutions to reflux 24 h, be washed till neutral after the dry activation namely realizing SBA-15 surface Si-OH;
(2) preparation of amino functional mesoporous material: the SBA-15 getting 0.25 g step (1) gained is scattered in 40 mL toluene, slow instillation 0.47 mL 3-aminopropyl triethoxysilane, logical nitrogen sealing also stirring and refluxing 10 h, products therefrom with toluene, ethanol washing, namely obtains amino functional mesoporous material after vacuum drying under 60 ° of C successively;
(3) preparation of the mesoporous material of grafted chain transfer agent: 0.073 g 2-(dodecyl trithiocarbonic acid ester group)-2 Methylpropionic acid (TTCA) is dissolved in 20 mL acetonitrile solutions, add the amino functional mesoporous material of 0.10 g step (2) gained, leave standstill in ice bath after ultrasonic 10 min; Add 82.5 mg N, the acetonitrile solution of N-dicyclohexylcarbodiimide, stirred at ambient temperature 10 h; Products therefrom acetonitrile wash, ambient temperature in vacuum is drying to obtain the mesoporous material of grafted chain transfer agent;
(4) preparation of cesium ion trace adsorbent: get 8.4 mg cesium chlorides (CsCl) and be dissolved in (methyl alcohol/acetonitrile=4/1 in 10 mL methyl alcohol and acetonitrile mixture, V/V), add 17 μ L methacrylic acids and 95 μ L GDMAs, add the mesoporous material of the grafted chain transfer agent of 50 mg step (3) gained again, 4 mg bis-isobutyronitriles are added after stirring, nitrogen protection, 60 ° of C water-bath 8 h; With the above-mentioned product of 0.1 mol/L EDTA solution washing 12 h to remove metal ion, repeated washing 5 times, and by the concentration of cesium ion in aas determination eluent, ensure that metal ion remaval is clean, the cesium ion trace adsorbent of gained is dried under 60 ° of C.
From Fig. 1 (a) and Fig. 1 (c), the cesium ion surface imprinted polymer of preparation maintains the regular corynebacterium structure of mesoporous SBA-15; The partial enlargement transmission electron microscope picture (Fig. 1 (b) and Fig. 1 (d)) on the two surface then describes RAFT imprinted polymer thin layer preferably and is effectively grafted to the surface of mesoporous SBA-15 and obtained Cs (I) ion blotting adsorbent maintains the excellent pore passage structure of matrix SBA-15 well.
Dynamic Adsorption is tested: 0.1 g cesium ion trace adsorbent is loaded Dynamic Adsorption post, pass into deionized water 10 min that pH is 6, after deionized water flows out completely, 10 mg/L cesium ion solution (pH=6) are passed into adsorption column, and be respectively 1.0 with peristaltic pump control loading flow velocity, 3.0, 5.0 mL/min, the temperature being controlled metal ion solution by extraneous recirculated water is respectively 25, 35, 55 ° of C, efflux is connect continuously with 10 mL color-comparison tubes, sample interval is 5, 8, 12, 15, 30, 45, 60, 75, 90, 120, , 150, 180, 360, 720 min, and connect sample Cs (I) concentration by atomic absorption spectrophotometer (FAAS) mensuration.
Result shows, 25 ° of C, flow velocity 1.0 mL min
-1time record connect sample Cs (I) equilibrium adsorption capacity be 6.18 mg/g, and reach balance when T=70 min.Through comparing discovery, temperature is lower, and flow velocity is less, and adsorption capacity is larger, and adsorption equilibrium required time is longer.
Static selective absorption experiment: preparation Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II) and object ion Cs (
) mixed liquor, the concentration of often kind of ion is 10 mg/L, and the solution getting the above-mentioned preparation of 25 mL, in colorimetric cylinder, is 6.0 by watery hydrochloric acid or weak aqua ammonia adjust ph, add 20 mg Cs (
) ion imprinted polymer, test fluid is placed in 25 ° of C water-baths and leaves standstill 12 h, centrifugation obtains supernatant, measures not by each concentration of metal ions adsorbed with atomic absorption spectrum and plasma emission spectrometer.
Result shows, Cs (I)-IIP shows good recognition performance to Cs (I), wherein Cs (I) is respectively 5.24 relative to the selectivity factor of competitive Adsorption ion Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II), 5.12,5.78,3.38,7.32, and 6.89, but not trace adsorbent NIP shows very poor adsorptive selectivity to Cs (I), its corresponding selection property coefficient is respectively 1.38,0.69,1.05,2.14,1.31,0.85.
Embodiment 2:
(1) mesoporous material SBA-15 is carried out purifying and activation: take 2 mg SBA-15 and leave standstill aging 24 h under 80 ° of C, then fully wash by deionized water, 50 h that finally reflux in ethanol remove the SBA-15 that residual template obtains purifying; SBA-15 after purifying is placed in 2.0 mol/L hydrochloric acid solutions to reflux 24 h, be washed till neutral after the dry activation namely realizing SBA-15 surface Si-OH;
(2) preparation of amino functional mesoporous material: the SBA-15 getting 0.5 g step (1) gained is scattered in 40 mL toluene, slow instillation 0.94 mL 3-aminopropyl triethoxysilane, logical nitrogen sealing also stirring and refluxing 15 h, products therefrom with toluene, ethanol washing, namely obtains amino functional mesoporous material after vacuum drying under 60 ° of C successively;
(3) preparation of the mesoporous material of grafted chain transfer agent: 0.146 g 2-(dodecyl trithiocarbonic acid ester group)-2 Methylpropionic acid (TTCA) is dissolved in 20 mL acetonitrile solutions, add the amino functional mesoporous material of 0.15 g step (2) gained, leave standstill in ice bath after ultrasonic 10 min; Add 123.8 mg N, the acetonitrile solution of N-dicyclohexylcarbodiimide, stirred at ambient temperature 15 h; Products therefrom acetonitrile wash, ambient temperature in vacuum is drying to obtain the mesoporous material of grafted chain transfer agent;
(4) preparation of cesium ion trace adsorbent: get 16.8 mg cesium chlorides (CsCl) and be dissolved in (methyl alcohol/acetonitrile=4/1 in 10 mL methyl alcohol and acetonitrile mixture, V/V), add 34 μ L methacrylic acids and 190 μ L GDMAs, add the mesoporous material of the grafted chain transfer agent of 75 mg step (3) gained again, 6 mg bis-isobutyronitriles are added after stirring, nitrogen protection, 60 ° of C water-bath 8 h; With the above-mentioned product of 0.1 mol/L EDTA solution washing 12 h to remove metal ion, repeated washing 5 times, and by the concentration of cesium ion in aas determination eluent, ensure that metal ion remaval is clean, the cesium ion trace adsorbent of gained is dried under 60 ° of C.
Dynamic Adsorption is tested: 0.1 g cesium ion trace adsorbent is loaded Dynamic Adsorption post, pass into deionized water 10 min that pH is 6, after deionized water flows out completely, 10 mg/L cesium ion solution (pH=6) are passed into adsorption column, and be respectively 1.0 with peristaltic pump control loading flow velocity, 3.0, 5.0 mL/min, the temperature being controlled metal ion solution by extraneous recirculated water is respectively 25, 35, 55 ° of C, efflux is connect continuously with 10 mL color-comparison tubes, sample interval is 5, 8, 12, 15, 30, 45, 60, 75, 90, 120, , 150, 180, 360, 720 min, and connect sample Cs (I) concentration by atomic absorption spectrophotometer (FAAS) mensuration.
Result shows, 25 ° of C, flow velocity 1.0 mL min
-1time record connect sample Cs (I) equilibrium adsorption capacity be 6.33 mg/g, and reach balance when T=90 min.Through comparing discovery, temperature is lower, and flow velocity is less, and adsorption capacity is larger, and adsorption equilibrium required time is longer.
Static selective absorption experiment: preparation Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II) and object ion Cs (
) mixed liquor, the concentration of often kind of ion is 10 mg/L, and the solution getting the above-mentioned preparation of 25 mL, in colorimetric cylinder, is 6.0 by watery hydrochloric acid or weak aqua ammonia adjust ph, add 20 mg Cs (
) ion imprinted polymer, test fluid is placed in 25 ° of C water-baths and leaves standstill 12 h, centrifugation obtains supernatant, measures not by each concentration of metal ions adsorbed with atomic absorption spectrum and plasma emission spectrometer.
Result shows, Cs (I)-IIP shows good recognition performance to Cs (I), wherein Cs (I) is respectively 7.67 relative to the selectivity factor of competitive Adsorption ion Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II), 8.72,9.31,5.73,11.25 with 8.54, but not trace adsorbent NIP shows very poor adsorptive selectivity to Cs (I), its corresponding selection property coefficient is respectively 0.97,1.26,1.24,0.77,0.95,1.15.
Embodiment 3:
(1) mesoporous material SBA-15 is carried out purifying and activation: take 2 mg SBA-15 and leave standstill aging 48 h under 80 ° of C, then fully wash by deionized water, 72 h that finally reflux in ethanol remove the SBA-15 that residual template obtains purifying; SBA-15 after purifying is placed in 3.0 mol/L hydrochloric acid solutions to reflux 24 h, be washed till neutral after the dry activation namely realizing SBA-15 surface Si-OH;
(2) preparation of amino functional mesoporous material: the SBA-15 getting 0.75 g step (1) gained is scattered in 40 mL toluene, slow instillation 1.41 mL 3-aminopropyl triethoxysilane, logical nitrogen sealing also stirring and refluxing 20 h, products therefrom with toluene, ethanol washing, namely obtains amino functional mesoporous material after vacuum drying under 60 ° of C successively;
(3) preparation of the mesoporous material of grafted chain transfer agent: 0.219 g 2-(dodecyl trithiocarbonic acid ester group)-2 Methylpropionic acid (TTCA) is dissolved in 20 mL acetonitrile solutions, add the amino functional mesoporous material of 0.2 g step (2) gained, leave standstill in ice bath after ultrasonic 10 min; Add 165.0 mg N, the acetonitrile solution of N-dicyclohexylcarbodiimide, stirred at ambient temperature 20 h; Products therefrom acetonitrile wash, ambient temperature in vacuum is drying to obtain the mesoporous material of grafted chain transfer agent;
(4) preparation of cesium ion trace adsorbent: get 25.2 mg cesium chlorides (CsCl) and be dissolved in (methyl alcohol/acetonitrile=4/1 in 10 mL methyl alcohol and acetonitrile mixture, V/V), add 51 μ L methacrylic acids and 285 μ L GDMAs, add the mesoporous material of the grafted chain transfer agent of 100 mg step (3) gained again, 8 mg bis-isobutyronitriles are added after stirring, nitrogen protection, 60 ° of C water-bath 8 h; With the above-mentioned product of 0.1 mol/L EDTA solution washing 12 h to remove metal ion, repeated washing 5 times, and by the concentration of cesium ion in aas determination eluent, ensure that metal ion remaval is clean, the cesium ion trace adsorbent of gained is dried under 60 ° of C.
Dynamic Adsorption is tested: 0.1 g cesium ion trace adsorbent is loaded Dynamic Adsorption post, pass into deionized water 10 min that pH is 6, after deionized water flows out completely, 10 mg/L cesium ion solution (pH=6) are passed into adsorption column, and be respectively 1.0 with peristaltic pump control loading flow velocity, 3.0, 5.0 mL/min, the temperature being controlled metal ion solution by extraneous recirculated water is respectively 25, 35, 55 ° of C, efflux is connect continuously with 10 mL color-comparison tubes, sample interval is 5, 8, 12, 15, 30, 45, 60, 75, 90, 120, , 150, 180, 360, 720 min, and connect sample Cs (I) concentration by atomic absorption spectrophotometer (FAAS) mensuration.
Result shows, 25 ° of C, flow velocity 1.0 mL min
-1time record connect sample Cs (I) equilibrium adsorption capacity be 6.24 mg/g, and reach balance when T=120 min.Through comparing discovery, temperature is lower, and flow velocity is less, and adsorption capacity is larger, and adsorption equilibrium required time is longer.
Static selective absorption experiment: preparation Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II) and object ion Cs (
) mixed liquor, the concentration of often kind of ion is 10 mg/L, and the solution getting the above-mentioned preparation of 25 mL, in colorimetric cylinder, is 6.0 by watery hydrochloric acid or weak aqua ammonia adjust ph, add 20 mg Cs (
) ion imprinted polymer, test fluid is placed in 25 ° of C water-baths and leaves standstill 12 h, centrifugation obtains supernatant, measures not by each concentration of metal ions adsorbed with atomic absorption spectrum and plasma emission spectrometer.
Result shows, Cs (I)-IIP shows good recognition performance to Cs (I), wherein Cs (I) is respectively 4.67 relative to the selectivity factor of competitive Adsorption ion Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II), 6.83,7.86,5.23,4.87,7.63, but not trace adsorbent NIP shows very poor adsorptive selectivity to Cs (I), its corresponding selection property coefficient is respectively 0.54,0.97,1.56,2.01,1.09,0.93.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (8)
1. a preparation method for activity/controlled mesoporous material surface ion imprinted polymer, is characterized in that comprising the steps:
I, mesoporous material SBA-15 is carried out purifying and activation;
II, the preparation of amino functional mesoporous material: above-mentioned SBA-15 and silane coupler are refluxed in toluene under oxygen free condition, product is through washing, drying;
III, the preparation of the mesoporous material of grafted chain transfer agent: above-mentioned amino functional mesoporous material is added in the acetonitrile solution 1 of chain-transferring agent, ultrasonic rear ice bath leaves standstill, and adds N, the acetonitrile solution 2 of N-dicyclohexylcarbodiimide, react under room temperature, product is through washing, drying;
IV, the preparation of ion imprinted polymer: the mesoporous material of template ion, function monomer, crosslinking agent, above-mentioned grafted chain transfer agent is stirred in methyl alcohol and acetonitrile mixture, add initator, in water-bath under oxygen free condition, also detect to metal ion washes clean with EDTA solution washing, dry product.
2. method as claimed in claim 1, is characterized in that described SBA-15 purifying and activation method are: SBA-15 is left standstill aging 12 ~ 48 h under 80 ° of C, and spend deionized water, 18 ~ 72 h that reflux in ethanol obtain the SBA-15 of purifying; Being placed on concentration is 24 h that reflux in 1.0 ~ 3.0 mol/L hydrochloric acid solutions, is washed till neutral rear dry.
3. method as claimed in claim 1, it is characterized in that, silane coupler described in step II is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane;
Described toluene consumption is that every 6.25 ~ 18.75 g SBA-15 are scattered in 1 L toluene, and described silane coupled agent concentration is 0.05 ~ 0.15 mol/L;
Described return time is 10 ~ 20 h.
4. method as claimed in claim 1, it is characterized in that, chain-transferring agent described in step III is 2-(dodecyl trithiocarbonic acid ester group)-2 Methylpropionic acid (TTCA);
Described acetonitrile content is that every 5.0 ~ 10.0 g amino functional mesoporous materials are placed in 1 L acetonitrile solution, and the concentration of described chain-transferring agent is 0.01 ~ 0.03 mol/L, and described N, N-dicyclohexylcarbodiimide concentration in acetonitrile 2 is 0.04 ~ 0.08 mol/L;
The described reaction time is 10 ~ 20 h.
5. method as claimed in claim 1, it is characterized in that, template ion described in step IV is for being provided by soluble metallic salt, described function monomer is methacrylic acid, described crosslinking agent is ethylene glycol dimethacrylate or N, N '-methylene-bisacrylamide, described initator is azodiisobutyronitrile;
In described mixed liquor, the volume ratio of methyl alcohol and acetonitrile is 4:1, described template ion concentration is 5.0 ~ 15.0 mmol/L, the concentration of described function monomer and crosslinking agent is respectively 20.0 ~ 60.0 mmol/L and 50.0 ~ 150.0 mmol/L, described initiator amount is that the mesoporous material of every 50 ~ 100 mg grafted chain transfer agents adds 4 ~ 8 mg initators, and the concentration of described EDTA solution is 0.1 mol/L;
Described bath temperature is 55 ~ 65 ° of C, and the water-bath time is 6 ~ 24 h.
6. as method as described in any one in claim 1-5, it is characterized in that, described template ion at least comprises nickel, iron, caesium, copper, strontium, mercury, cobalt, cadmium, manganese, zinc.
7. as method as described in any one in claim 1-6 prepares activity/controlled mesoporous material surface ion imprinted polymer.
8. the application of activity/controlled mesoporous material surface ion imprinted polymer corresponding ion in adsorption aqueous solution as claimed in claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410467787.2A CN104258826B (en) | 2014-09-15 | 2014-09-15 | A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410467787.2A CN104258826B (en) | 2014-09-15 | 2014-09-15 | A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104258826A true CN104258826A (en) | 2015-01-07 |
| CN104258826B CN104258826B (en) | 2016-08-17 |
Family
ID=52150474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410467787.2A Expired - Fee Related CN104258826B (en) | 2014-09-15 | 2014-09-15 | A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104258826B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877090A (en) * | 2015-05-12 | 2015-09-02 | 江苏大学 | Method for preparing ion imprinting polymer by virtue of ultraviolet induced polymerization at room temperature and application of ion imprinting polymer |
| CN105148851A (en) * | 2015-09-28 | 2015-12-16 | 太原理工大学 | Preparation method and application of carbamido functionalized cadmium ion surface print adsorbent |
| CN105396555A (en) * | 2015-11-04 | 2016-03-16 | 安阳工学院 | Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions |
| CN105749879A (en) * | 2016-03-04 | 2016-07-13 | 江苏大学 | Preparation method of pore filling type molecule/ion double-site imprinted polymer |
| CN108246265A (en) * | 2017-11-22 | 2018-07-06 | 广东工业大学 | The synthesis of graphene oxide-mesoporous silicon surface hexavalent chromium imprinted material and the method applied in water process |
| CN111707633A (en) * | 2020-06-24 | 2020-09-25 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | Simultaneous Cu detection by organic-inorganic mesoporous hybrid material2+、Co2+、Ni2+Method of ionizing |
| CN112295549A (en) * | 2020-09-11 | 2021-02-02 | 中南大学 | Adsorbent for selectively separating gold and preparation method and application thereof |
| CN114345300A (en) * | 2022-01-07 | 2022-04-15 | 万华化学集团股份有限公司 | Adsorbent and preparation method thereof, and method for purifying cyclic olefin polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050281878A1 (en) * | 2002-10-29 | 2005-12-22 | Cowieson David R | Process |
| CN103433005A (en) * | 2013-08-26 | 2013-12-11 | 江苏大学 | Preparation method for triglycine functionalized mesoporous material surface imprinting adsorbent |
| 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 |
| CN103629393A (en) * | 2013-12-26 | 2014-03-12 | 大连深蓝泵业有限公司 | Conical surface sealing suction bottom valve matched with low-temperature immersed pump |
-
2014
- 2014-09-15 CN CN201410467787.2A patent/CN104258826B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050281878A1 (en) * | 2002-10-29 | 2005-12-22 | Cowieson David R | Process |
| CN103433005A (en) * | 2013-08-26 | 2013-12-11 | 江苏大学 | Preparation method for triglycine functionalized mesoporous material surface imprinting adsorbent |
| 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 |
| CN103629393A (en) * | 2013-12-26 | 2014-03-12 | 大连深蓝泵业有限公司 | Conical surface sealing suction bottom valve matched with low-temperature immersed pump |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877090B (en) * | 2015-05-12 | 2017-08-04 | 江苏大学 | A kind of room temperature ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer |
| CN104877090A (en) * | 2015-05-12 | 2015-09-02 | 江苏大学 | Method for preparing ion imprinting polymer by virtue of ultraviolet induced polymerization at room temperature and application of ion imprinting polymer |
| CN105148851A (en) * | 2015-09-28 | 2015-12-16 | 太原理工大学 | Preparation method and application of carbamido functionalized cadmium ion surface print adsorbent |
| CN105396555A (en) * | 2015-11-04 | 2016-03-16 | 安阳工学院 | Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions |
| CN105749879B (en) * | 2016-03-04 | 2018-08-10 | 江苏大学 | A kind of preparation method of duct filled-type molecular/ionic double site imprinted polymer |
| CN105749879A (en) * | 2016-03-04 | 2016-07-13 | 江苏大学 | Preparation method of pore filling type molecule/ion double-site imprinted polymer |
| CN108246265A (en) * | 2017-11-22 | 2018-07-06 | 广东工业大学 | The synthesis of graphene oxide-mesoporous silicon surface hexavalent chromium imprinted material and the method applied in water process |
| CN108246265B (en) * | 2017-11-22 | 2021-07-06 | 广东工业大学 | Synthesis of graphene oxide-mesoporous silicon surface hexavalent chromium imprinting material and method for applying same in water treatment |
| CN111707633A (en) * | 2020-06-24 | 2020-09-25 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | Simultaneous Cu detection by organic-inorganic mesoporous hybrid material2+、Co2+、Ni2+Method of ionizing |
| CN111707633B (en) * | 2020-06-24 | 2023-03-21 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | Simultaneous Cu detection by organic-inorganic mesoporous hybrid material 2+ 、Co 2+ 、Ni 2+ Method of ionizing |
| CN112295549A (en) * | 2020-09-11 | 2021-02-02 | 中南大学 | Adsorbent for selectively separating gold and preparation method and application thereof |
| CN114345300A (en) * | 2022-01-07 | 2022-04-15 | 万华化学集团股份有限公司 | Adsorbent and preparation method thereof, and method for purifying cyclic olefin polymer |
| CN114345300B (en) * | 2022-01-07 | 2023-07-14 | 万华化学集团股份有限公司 | Adsorbent and preparation method thereof, and method for purifying cycloolefin polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104258826B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104258826A (en) | Active/controllable mesoporous material ion-surface imprinted polymer as well as preparation method and application of ion-surface imprinted polymer | |
| Gao et al. | Recent advances and future trends in the detection of contaminants by molecularly imprinted polymers in food samples | |
| Qin et al. | Surface-modified polystyrene beads as photografting imprinted polymer matrix for chromatographic separation of proteins | |
| Shi et al. | Molecularly imprinted polymer microspheres for solid-phase extraction of chloramphenicol residues in foods | |
| Díaz-Álvarez et al. | Molecularly imprinted polymer monolith containing magnetic nanoparticles for the stir-bar sorptive extraction of thiabendazole and carbendazim from orange samples | |
| Rajabi et al. | Preparation of a novel potassium ion imprinted polymeric nanoparticles based on dicyclohexyl 18C6 for selective determination of K+ ion in different water samples | |
| Guo et al. | Chemically modified chitosan beads as matrices for adsorptive separation of proteins by molecularly imprinted polymer | |
| Zhu et al. | Highly efficient adsorption of Hg (II) and Pb (II) onto chitosan-based granular adsorbent containing thiourea groups | |
| Li et al. | Selective recognition of veterinary drugs residues by artificial antibodies designed using a computational approach | |
| Wang et al. | Enhanced binding capacity of boronate affinity adsorbent via surface modification of silica by combination of atom transfer radical polymerization and chain-end functionalization for high-efficiency enrichment of cis-diol molecules | |
| CN102711978A (en) | Porous polymer monoliths, processes for preparation and use thereof | |
| Tobiasz et al. | Improvement of copper FAAS determination conditions via preconcentration procedure with the use of salicylaldoxime complex trapped in polymer matrix | |
| Song et al. | Molecularly imprinted solid-phase extraction of glutathione from urine samples | |
| CN108250360B (en) | Aptamer-molecularly imprinted fluorescent sensor with dual-specificity recognition on kanamycin and preparation method and application thereof | |
| Neagu et al. | Adsorption studies of some inorganic and organic salts on new zwitterionic ion exchangers with carboxybetaine moieties | |
| CN108003287B (en) | Preparation method of protein affinity imprinted hydrogel polymer based on acrylamide metal chelating monomer | |
| Anirudhan et al. | Investigation of the extraction of hemoglobin by adsorption onto nanocellulose-based superabsorbent composite having carboxylate functional groups from aqueous solutions: kinetic, equilibrium, and thermodynamic profiles | |
| Tu et al. | Molecularly imprinted dispersive solid-phase microextraction sorbents for direct and selective drug capture from the undiluted bovine serum | |
| Lv et al. | Fast clean-up and selective enrichment of florfenicol in milk by restricted access media molecularly imprinted magnetic microspheres based on surface-initiated photoiniferter-mediated polymerization | |
| Wikberg et al. | Grafting of silica with sulfobetaine polymers via aqueous reversible addition fragmentation chain transfer polymerization and its use as a stationary phase in HILIC | |
| CN106977648B (en) | Method for preparing bisphenol A molecularly imprinted material from functional monomer containing template molecular structure | |
| Zarco-Fernández et al. | A new specific polymeric material for mercury speciation: Application to environmental and food samples | |
| CN106519150B (en) | A kind of preparation method of fluorescence polarization fluorescence magnetic molecular engram sensor | |
| CN112552469B (en) | Preparation method of bisphenol A magnetic molecularly imprinted polymer and application of bisphenol A magnetic molecularly imprinted polymer in bisphenol A fluorescence detection | |
| CN103623788A (en) | Preparation method of magnetic mesoporous free radical controlled polymer ion printing adsorbing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20180915 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |