CN104877090B - A kind of room temperature ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer - Google Patents
A kind of room temperature ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer Download PDFInfo
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Abstract
The present invention relates to a kind of ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer, belong to material preparation, isolation technics and environmental treatment field.Imprinted polymer of the present invention can be as the heavy metal ion in the selective Dynamic Separation waste water of solid phase extraction adsorbentses, the present invention modifies method in host material (Silica) surface introducing vinyl by two steps first, obtain Silica APTS AC, finally using Silica APTS AC as matrix, Co (II) is template ion, benzophenone (BP) is light trigger, at ambient temperature, a kind of hud typed ion imprinted polymer adsorbent has been synthesized under ultraviolet light, its absorption property to Co (II) is investigated, the adsorbent can have good separating effect under room temperature environment, have adsorption capacity big Co (II), selectivity is high, separating effect is notable, reuse advantage often.This provides a class new method for the heavy metal element (such as Co (II)) in selective separation enrichment environmental sample.
Description
Technical field
The present invention relates to a kind of ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer, belong to material system
Standby, isolation technics and environmental treatment field.
Background technology
With the sharp increase of population in the world and developing rapidly for modern industry, the mankind are to the demand of water resource with surprising
Speed is increasing, and the discharge capacity for the waste water that various industrial productions and life activity are produced also increasingly increases.Wherein, mining and metallurgy, machinery
What is produced in the industry such as manufacture, chemical industry, electronics, instrument in many production processes contains heavy metal ion（Cadmium, chromium, copper, mercury, nickel, cobalt
Deng）Waste water is the pollution sources to the heavy metal ion of water environment pollution.When the waste water containing these heavy metal ion pollutants not
Through handling or handling below standard just arrange to nature so that water body and soil are caused water body and soil by different degrees of pollution
Loamy texture amount drastically deteriorates, and surface water and groundwater is by different degrees of pollution.The water pollution thereby resulted in is that our times is each
One of environmental problem that ground is faced.Metal pollutant is a class environmental persistence pollutant, and accumulation property is permanent in vivo
In the presence of to human health and the ecosystem with very strong poisonous effect, it is therefore necessary to which the metal pollutant in environment is carried out
Analysis in time, detection and effectively processing., must but metal contaminant content in environmental sample is low, property is similar, matrix is complicated
Rational method must be found the metal pollutant in environmental sample is carried out to separate/preenrichment.Therefore, removal is efficiently separated water-soluble
Heavy metal element tool is of great significance in liquid.Wherein conventional separation method has ion exchange to extract skill with adsorption solid phase
Art, solvent extraction technology and chemical precipitation method etc..These methods respectively have particular advantages, but its limitation is also individually present.Such as from
Son exchanges poor with adsorption solid phase abstraction technique heat endurance, and cation exchange groups are easily lost at high temperature, are dropped under radiation effects
Solution, adsorption capacity is low；Solvent extraction technology largely uses organic solvent, is also easy to produce secondary pollution.Therefore develop selectivity it is good,
The adsorbent that adsorption capacity is high, simple to operate, regenerability is excellent, setting up specific nuclear waste transmutation adsorbent has important meaning
Justice.
The appearance and development of ionic imprinting technique (Ion Imprinting Technique, IIT) are expected to solve this
Problem.Ionic imprinting technique, is used as point of molecular imprinting technology (Molecular Imprinting Technique, MIT)
Branch, be metal ion to be separated and function monomer are carried out by chelation it is pre-assembled, with crosslinking agent copolymerization be combined
Thing, is selected after appropriate eluant, eluent elutes template ion, just formd in polymer on binding site and space structure with
The three-dimensional trace hole that template ion is matched completely, is capable of the object ion in the identification complex environment of high selectivity.Ion prints
Mark polymer (Ion Imprinted Polymers, IIP) has had both the advantage of bio-identification system and Chemical recognition system,
With anti-adverse environment, selectivity height, good stability, high mechanical strength, prepares simple the features such as, it is alternative to recognize and enrichment
Object in complex sample, therefore had a good application prospect in complex environment.Wherein surface ion imprinted polymer
(Surface Ion Imprinted Polymers, SIIP) is even more the binding site for solving and being caused after highly cross-linked polymerization
Heterogeneity, accessibility are poor, mass transfer rate is slow, the low problem of site utilization rate, can realize imprinted polymer and template ion
Between quickly combine and separate, reduce influence of the non-specific adsorption to selectivity, be specific ion from similar mixed of structure
Separated in compound there is provided feasible effective solution route.This is also carried effectively to remove heavy metal element in the environment aqueous solution
New method is supplied.
Silica-base material has the advantages that good mechanical performance, sour environment stability are high, is difficult to be swelled, and is conventional table
Face Blotting matrix material.First its surface is modified before polymerization, ethylenic linkage is introduced, then by the way of radical polymerization
Carry out the preparation of imprinted polymer.Wherein, it is that conventional one kind is gathered using high temperature thermal initiation using azodiisobutyronitrile as initiator
Conjunction mode, the higher temperature of its polymerization process initiation generation free radical needs (>60°C).Spivak has found that trace gathers under study for action
The expressive ability of compound such as specific recognition and high selectivity are mainly the result of imprinted cavity shape selection（Spivak D,
Gilmore M A, Shea K J. Evaluation of binding and origins of specificity of 9-
ethyladenine imprinted polymers[J]. Journal of the American Chemical Society,
1997, 119(19): 4388-4393.）, and it was found that this special combination site formed between monomer molecule and template
Imprinted cavity is more favored in being formed at low temperature（Spivak D, Shea K J. Molecular imprinting of
carboxylic acids employing novel functional macroporous polymers [J]. The
Journal of organic chemistry, 1999, 64(13): 4627-4634.）.In addition, Piletsky have studied it is poly-
Close influence of the temperature to trace polymerization physical performance, as a result find reduction polymerization temperature can be obviously improved polymer affinity and
Specificity（Piletsky S A, Piletska E V, Karim K, et al. Polymer cookery: influence
of polymerization conditions on the performance of molecularly imprinted
polymers [J]. Macromolecules, 2002, 35(19): 7499-7504.）.Piletska researchs are it has also been found that poly-
Close temperature related to being in conjunction with the Optimal Temperature in experiment, i.e., the imprinted polymer synthesized under high temperature table in high temperature environments
Now preferably, the imprinted polymer synthesized under low temperature is preferable in low temperature environment performance（Piletska E V, Guerreiro A R,
Whitcombe M J, et al. Influence of the polymerization conditions on the
performance of molecularly imprinted polymers [J]. Macromolecules, 2009, 42
(14): 4921-4928.）.Obviously, this " temperature memory " of imprinted polymer has very big reference in actual applications
And directive significance.The processing of environment water pollution such as heavy metal ion is often carried out at room temperature, if the adsorbent meeting synthesized under high temperature
Weaken its expressive ability, and heating up strengthens its adsorption effect and can then increase running cost.So, research one kind can in low temperature or
The method that person synthesizes the ion imprinted polymer for having outstanding absorption property to metal ion at room temperature has certain practicality and can
Row.
At present, light initiation polymerization has been widely used in light and consolidated because its polymerization process time is short, temperature is low and with low cost
During change（Deng J, Wang L, Liu L, et al. Developments and new applications of
UV-induced surface graft polymerizations [J]. Progress in Polymer Science,
2009, 34(2): 156-193.）.In recent years, light initiation polymerization was also gradually applied to the building-up process of molecularly imprinted polymer
In.Preparation more particularly to temperature than more sensitive imprinted polymer, such as protein-imprinted polymer（Sunayama
H, Takeuchi T. Molecularly Imprinted Protein Recognition Cavities Bearing
Exchangeable Binding Sites for Postimprinting Site-Directed Introduction of
Reporter Molecules for Readout of Binding Events [J]. ACS applied materials &
interfaces, 2014, 6(22): 20003-20009.）.But in the synthesis of ion imprinted polymer, drawn using light
The mode of hair polymerization was not yet reported.
The content of the invention
The present invention is overcomes defect present in prior art, it is therefore an objective to provide a kind of room temperature it is ultraviolet trigger polymerization prepare from
The method of sub- imprinted polymer.
The technical solution adopted by the present invention is：A diameter of 100 ~ 400nm titanium dioxide is prepared by St ber methods first
Silicon grain（Silica）, vinyl is introduced in particle surface using two steps modification method after being activated, Silica-APTS- is obtained
AC.Then using Silica-APTS-AC as host material, Co (II) be template ion, acrylamide (AM) be function monomer, N,
N- methylene-bisacrylamides（MBA）For crosslinking agent, benzophenone (BP) is light trigger, and methanol is dispersant, purple in room temperature
Under outer light (main crest is 365nm) irradiation, it is prepared for being capable of Co (II) a kind of ion imprinted polymer of Selective Separation.
A kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer of room temperature, is carried out according to the following steps：
(1) host material Silica preparation
In single-necked flask, 2 ~ 6 mL water, 5 ~ 15 mL ammoniacal liquor are separately added into（28%）, it is close in 30 ~ 90 mL absolute ethyl alcohols
Seal the min of magnetic agitation 10；Then 3 ~ 9 mL TEOS are taken to be placed in the beaker containing 20 ~ 60 mL absolute ethyl alcohols；It is well mixed
Afterwards, the mixed liquor in beaker is carefully rapidly added in single-necked flask, sealing continues to stir 24 h at room temperature；After reaction terminates,
Centrifuge, and with ethanol and water washing several times until solution is placed in vacuum drying chamber in neutrality, 50 °C are dried in vacuo
24 h dry for standby.
(2) silica surface modified by vinyl (Silica-APTS-AC)
The Silica prepared in step (1) is placed in round-bottomed flask, 50 mL concentration of addition are 3 mol L-1Hydrochloric acid, its
The middle mass fraction for controlling Silica is 0.20 ~ 1.0 %, and flow back 24 h, then filters, with secondary deionized water cyclic washing extremely
Take out standby after neutrality, 80 °C of 12 h of vacuum drying, the Silica activated.
Then take Silica and 3- aminopropyl triethoxysilanes (APTS) after activation be placed in 50 ~ 150mL without water beetle
In benzene, wherein the ratio for controlling Silica and APTS is 1g:5-20mL, flow back 24h, after reaction terminates, with toluene and ethanol point
Xi Di not be three times, then be dispersed in again standby in 50 ~ 150mL dry toluene.
Finally, it is dispersed with above-mentioned in the Silica anhydrous toluene solutions after APTS is modified, adds 0.5 ~ 5.0 g anhydrous
Potassium carbonate, ultrasonic 30min；Then 1h is stirred in ice bath, treats that temperature is down to zero, 0.5 is added dropwise using constant pressure funnel ~
After 5mL acrylic acid (AC), completion of dropping, nitrogen protection continues to react 12h at room temperature, that is, obtains Silica-APTS-AC；Reaction
After end, washed successively with dry toluene and absolute ethyl alcohol three times, take out standby after 50 °C of 24 h of vacuum drying.
(3) room temperature is ultraviolet triggers polymerization synthesis ion imprinted polymer（P-IIP）
The Silica-APTS-AC that will be obtained in step (2), cabaltous nitrate hexahydrate (Co (II)), acrylamide (AM), N,
N- methylene-bisacrylamides (MBA) and benzophenone (BP) mixing are added into the mixed solution of methanol-water, wherein controlling
Silica-APTS-AC mass fraction is 0.147 ~ 0.294%, and cobalt ions Co (II) concentration is 1.25 ~ 5.00 mmol L-1,
AM concentration is 7.5 ~ 30.0 mmol L-1, MBA concentration is 5.0 ~ 25.0 mmol L-1, BP concentration for 0.686 ~
1.372 mmol L-1, the mixed liquor 40mL of methanol-water, the wherein ratio of methanol and water are 3:1.After 30 min of ultrasound, lead to nitrogen
Sealed after deoxygenation 20min, be placed in the photochemical reaction instrument containing magnetic agitation, uviol lamp is high pressure of the main crest section in 365nm
Mercury lamp, instrument controlling temperature is 25 °C.It is passed through recirculation water, 2 ~ 12h of illumination.Wherein, benzophenone is used for light trigger, can be with
Free radical is produced under ultraviolet light, carries out Light lnduced Free Radicals polymerization, and light initiation polymerization can be in low temperature or room temperature ring
Carried out under border.Successively with methanol and each washing of deionized water difference five times after reaction, to remove unreacted AM and MBA and not
The template ion (Co (II)) of trace, is dried in vacuo under 50 °C, then with the mol L of 500 ~ 2000 mL 2-1Hydrochloric acid solution is washed
Template ion is removed, and is washed with deionized water to neutrality, then vacuum drying obtains surface ion imprinted polymer (P- under 50 °C
IIP)。
In above-mentioned technical scheme, it is its surface hydroxyl is lived that the silica dioxide granule of synthesis is flowed back with hydrochloric acid solution
Change.
Cabaltous nitrate hexahydrate described in above-mentioned technical proposal, it act as template ion.
Acrylamide described in above-mentioned technical proposal, it act as function monomer.
N described in above-mentioned technical proposal, N- methylene-bisacrylamide, it act as crosslinking agent.
Benzophenone described in above-mentioned technical proposal, it act as initiator.
Silica described in above-mentioned technical proposal, it act as host material.
3- aminopropyl triethoxysilanes described in above-mentioned technical proposal, it act as silane coupler.
Anhydrous potassium carbonate described in above-mentioned technical proposal, it act as acid binding agent.
Acrylic acid described in above-mentioned technical proposal, it act as acylating reagent.
The light-initiated polymerization methodses of room temperature described in such scheme, polymer is obtained its role is to quick, and can be
There is the surface ion imprinted polymer of outstanding expressive ability in practical application.
The non-trace ionomer of correspondence prepared by the present invention（P-NIP）Method is similar, but is not added with cabaltous nitrate hexahydrate.Institute
The P-NIP of preparation is used as blank control.
(4) absorption property analysis test
（One）Staticadsorption experiment：
By the Co of 25mL concentration knowns () solution is added in 25 mL colorimetric cylinders, is stood in water bath with thermostatic control, investigate and inhale
Initial concentration, solution ph, temperature, adsorption time and other metal ion disturbances of attached solution to trace adsorbent recognize Co (
) ability influence.After absorption, by centrifuging, the unadsorbed Co of supernatant liquor () concentration atomic absorption spectrophotometer
And plasma emission spectrometer (FAAS)（ICP）Determine, and calculate P-IIP adsorption capacity（Q e, mg/g）.
WhereinC 0(mg/L) andC e(mg/L) respectively be absorption before and after Co () concentration,W (g) it is adsorbent amount,V
(L) it is liquor capacity.
（Two）Selective absorption is tested
Selection Cu ()、Ni()、Pb()、Cd() be competitive Adsorption ion, be respectively configured four kinds of ions and Co ()
Binary liquid mixture, the concentration of every kind of ion is 5 mg/ L.The solution for taking 25 mL to configure is added in colorimetric cylinder, is separately added into
20 mg traces and non-trace adsorbent, test fluid are placed in 25 °C of water-bath and stand 12.0 h respectively.After standing, centrifugation point
From obtaining supernatant, the concentration plasma emission spectrometer of unadsorbed various competitive Adsorption substrates（ICP）Determine.
Advantage of the invention is that：
One kind that the present invention is prepared first can at ambient temperature, and the ultraviolet hud typed ion blotting for triggering polymerization synthesis gathers
Compound, and can have good separating effect under room temperature environment, have adsorption capacity big Co (II), selectivity is high, separation
Effect significantly, reuses advantage often.This is the heavy metal element Co (II) in selective separation enrichment environmental sample
There is provided a class new method.Advantage specifically has following three points：
（1）Effect of the imprinted polymer in application is mentioned in aforementioned background art with its polymerization temperature with associated
System, reduction polymerization temperature can substantially lift its expressive ability in low temperature environment.The general polymer is used as adsorbent
Under room temperature environment, so present invention research is a kind of can to synthesize the performance energy that can be obviously improved it in room temperature environment at room temperature
Power.
（2）Thermal-initiated polymerization is needed in hot environment, is unfavorable for the generation of imprinted sites, can be caused in imprinted polymer
Non-specific adsorption increase.To strengthen the specificity of imprinted polymer, its expressive ability is improved, the present invention takes room temperature light-initiated
Radical polymerization mode.
（3）Light lnduced Free Radicals polymerization has that reaction is quick, and the advantage such as initiation temperature is low and simple to operate, is following replacement
The promising mode of comparison of high temperature thermal-initiated polymerization.And at present, room temperature light initiation polymerization synthesis ion imprinted polymer does not have
Report, the present invention synthesizes other ion imprinted polymers for light initiation polymerization and provides a platform.
Brief description of the drawings
Fig. 1 is raw material and polymer infared spectrum in example 2, and a is Silica in figure；B is Silica-APTS；C is
Silica-APTS-AC；D is P-IIP.
Fig. 2 is silica scanning electron microscope (SEM) photograph and transmission electron microscope picture in example 2, and wherein a is silica scanning electron microscope (SEM) photograph；
B is silica transmission electron microscope picture.
Fig. 3 is the intermediate ion imprinted polymer scanning electron microscope (SEM) photograph of example 2 and transmission electron microscope picture, and wherein a polymerize for ion blotting
Thing scanning electron microscope (SEM) photograph；B is ion imprinted polymer transmission electron microscope picture.
Embodiment
With reference to specific implementation example, the present invention will be further described.
Embodiment 1：
(1) host material Silica preparation
In single-necked flask, 2 mL water, 5 mL ammoniacal liquor are separately added into（28%）, in 30 mL absolute ethyl alcohols, sealing magnetic is stirred
Mix 10 min.Then 3 mL TEOS are taken to be placed in the beaker containing 20 mL absolute ethyl alcohols.When well mixed after, this mixed liquor is small
The heart is rapidly added in single-necked flask, and sealing continues to stir 24 h at room temperature.After reaction terminates, centrifuge, and use second alcohol and water
Washing is several times until solution is placed in vacuum drying chamber in neutrality, and 50 °C are dried in vacuo 24 h dry for standby.
(2) silica surface modified by vinyl (Silica-APTS-AC)
The g of Silica 0.2 prepared in step (1) are placed in round-bottomed flask, 50 mL concentration of addition are 3 mol L-1
Hydrochloric acid, flow back 24 h, then filters, with secondary deionized water cyclic washing to neutrality, and 80 °C are dried in vacuo taking-up after 12 h.
Then Silica 0.1g and 0.5 mL 3- aminopropyl triethoxysilanes (APTS) after activation is taken to be placed in 50 mL
Dry toluene in, flow back 24h, reaction terminate after, washed respectively three times with toluene and ethanol, then be dispersed in 50 ~ 150mL again
Dry toluene in it is standby.
Toluene liquid again scattered is placed in flask with three necks,round bottom after being modified containing above-mentioned coupling agent, and adds 0.5 g
Anhydrous potassium carbonate, ultrasonic 30min.Then 1h is stirred in ice bath, treats that temperature is down to zero, is added dropwise using constant pressure funnel
After 0.5 mL acrylic acid (AC), completion of dropping, nitrogen protection continues to react 12h at room temperature, that is, obtains Silica-APTS-AC.
After reaction terminates, washed successively with dry toluene and absolute ethyl alcohol three times, take out standby after 50 °C of 24 h of vacuum drying.
(3) room temperature is ultraviolet triggers polymerization synthesis ion imprinted polymer（P-IIP）
Silica-APTS-AC in step (2) is taken into 0.05g, and 14.6 mg cabaltous nitrate hexahydrates (Co (II)), 21.3
Mg AM, 30.8 mg MBA, 5mg BP mixing is added into the mixed solution of 40mL methanol-waters, wherein controlling Silica-
APTS-AC mass fraction is 0.148%, and cobalt ions Co (II) concentration is 1.25 mmol L-1, AM concentration is 7.5 mmol
L-1, MBA concentration is 5 mmol L-1, BP concentration is 0.686 mmol L-1, the volume ratio of methanol and water is 3:1.Ultrasound
After 30 min, and sealed after nitrogen deoxygenation 20min, be placed in the photochemical reaction instrument containing magnetic agitation, uviol lamp is main crest
Section is in 365nm high-pressure sodium lamp, and instrument controlling temperature is 25 °C.It is passed through recirculation water, the h of illumination 6.After reaction successively with methanol and
Each washing of deionized water difference five times, to remove the template ion (Co of unreacted monomer and crosslinking agent and non-trace
(II)), it is dried in vacuo under 50 °C, then with the mol L of 500 mL 2-1Hydrochloric acid solution washes away template ion, and uses deionization
Neutrality is washed to, then vacuum drying obtains surface ion imprinted polymer (P-IIP) under 50 °C.
(4) adsorption test
It is respectively 1,3,5,10,15,20,30,50,100,150,200,250,300 and 400 to take 25 mL initial concentrations
Mg/L Co (II) solution is added in 25 mL colorimetric cylinders, is 5.0 with watery hydrochloric acid or weak aqua ammonia regulation pH value, is separately added into 10
Three groups of test fluids, are individually placed to 25, stood after 12 h in 35,45 °C of water-bath, centrifugation point by mg traces and non-trace adsorbent
From obtaining Co (II) concentration Atomic Absorption Spectrometry not to be adsorbed in supernatant liquor, supernatant liquor, and according to result meter
Calculate adsorption capacity.As a result it is 97.48 mg/g to show saturated extent of adsorption of the P-IIPs under 25 °C, is inhaled much larger than in non-trace
Attached dose of 22.64 mg/g.
(5) selectivity experiment
Co() and Cu ()、Ni()、Pb()、Cd() mixing binary system competitive Adsorption, take 25 mL configure
Good concentration for 5 mg/L Co ()/M() mixed solution is added in colorimetric cylinder, and pH value is adjusted with watery hydrochloric acid or weak aqua ammonia
For 5.0,20 mg P-IIP and P-NIP are separately added into.Test fluid is placed in 25 °C of water-bath and stands 12 h.It is then centrifuged for point
From obtaining CoII not to be adsorbed in supernatant liquor, supernatant liquor) and other competitive Adsorption ion M () concentration surveyed with ICP
It is fixed, adsorption capacity is calculated according to result.As a result show that 20 mg P-IIP show good recognition performance to Co (II), its
Middle Co (II) relative to competitive Adsorption ion Cu ()、Ni()、Pb()、Cd() selectivity factor be respectively 4.32,
7.16,12.14 and 6.64, rather than trace adsorbent P-NIP shows very poor adsorptive selectivity to Co (II).
Embodiment 2：
(1) host material Silica preparation
In single-necked flask, 4 mL water, 10 mL ammoniacal liquor are separately added into（28%）, in 60 mL absolute ethyl alcohols, sealing magnetic is stirred
Mix 10 min.Then 6 mL TEOS are taken to be placed in the beaker containing 40 mL absolute ethyl alcohols.When well mixed after, this mixed liquor is small
The heart is rapidly added in single-necked flask, and sealing continues to stir 24 h at room temperature.After reaction terminates, centrifuge, and use second alcohol and water
Washing is several times until solution is placed in vacuum drying chamber in neutrality, and 50 °C are dried in vacuo 24 h dry for standby.
(2) silica surface modified by vinyl (Silica-APTS-AC)
The Silica 0.5g prepared in step (1) are placed in round-bottomed flask, 50 mL concentration of addition are 3 mol L-1Salt
Acid, flow back 24 h, then filters, with secondary deionized water cyclic washing to neutrality, takes out standby after 80 °C of 12 h of vacuum drying
With.
Then Silica 0.1g and 2 mL 3- aminopropyl triethoxysilanes (APTS) after activation is taken to be placed in 50 mL's
In dry toluene, flow back 24h, after reaction terminates, is washed respectively three times with toluene and ethanol, then be dispersed in the anhydrous of 50mL again
It is standby in toluene.
The toluene liquid that Silica disperses again after being modified containing above-mentioned coupling agent is placed in flask with three necks,round bottom, and is added
2.0 g Anhydrous potassium carbonates, ultrasonic 30min.Then 1h is stirred in ice bath, treats that temperature is down to zero, using constant pressure funnel dropwise
Add after 2mL acrylic acid (AC), completion of dropping, nitrogen protection continues to react 12h at room temperature, that is, obtains Silica-APTS-AC.
After reaction terminates, washed successively with dry toluene and absolute ethyl alcohol three times, take out standby after 50 °C of 24 h of vacuum drying.
(3) room temperature is ultraviolet triggers polymerization synthesis ion imprinted polymer（P-IIP）
Silica-APTS-AC in step (2) is taken into 0.05g, and 29.2 mg cabaltous nitrate hexahydrates (Co (II)), 42.6
Mg AM, 77.0 mg MBA, 5mg BP mixing is added into the mixed solution of 40mL methanol-waters, wherein controlling Silica-
APTS-AC mass fraction is 0.147 %, and cobalt ions Co (II) concentration is 2.5 mmol L-1, AM concentration is 15 mmol
L-1, MBA concentration is 12.5 mmol L-1, BP concentration is 0.686 mmol L-1, the volume ratio of methanol and water is 3:1.
After 30 min of ultrasound, and sealed after nitrogen deoxygenation 20min, the photochemical reaction instrument containing magnetic agitation is placed in, based on uviol lamp
Crest section is in 365nm high-pressure sodium lamp, and instrument controlling temperature is 25 °C.It is passed through recirculation water, the h of illumination 4.First is used after reaction successively
Alcohol and deionized water difference it is each washing five times, to remove the template ion (Co of unreacted monomer and crosslinking agent and non-trace
(II)), it is dried in vacuo under 50 °C, then with the mol L of 1500 mL 2-1Hydrochloric acid solution washes away template ion, and uses deionization
Neutrality is washed to, then vacuum drying obtains surface ion imprinted polymer (P-IIP) under 50 °C.
(4) adsorption test
It is respectively 1,3,5,10,15,20,30,50,100,150,200,250,300 and 400 to take 25 mL initial concentrations
Mg/L Co (II) solution is added in 25 mL colorimetric cylinders, is 5.0 with watery hydrochloric acid or weak aqua ammonia regulation pH value, is separately added into 10
Three groups of test fluids, are individually placed to 25, stood after 12 h in 35,45 °C of water-bath, centrifugation point by mg traces and non-trace adsorbent
From obtaining Co (II) concentration Atomic Absorption Spectrometry not to be adsorbed in supernatant liquor, supernatant liquor, and according to result meter
Calculate adsorption capacity.As a result it is 116.62 mg/g to show saturated extent of adsorption of the P-IIPs under 25 °C, is almost four times in non-trace
29.53 mg/g of adsorbent.
(5) selectivity experiment
Co() and Cu ()、Ni()、Pb()、Cd() mixing binary system competitive Adsorption, take 25 mL configure
Good concentration for 5 mg/L Co ()/M() mixed solution is added in colorimetric cylinder, and pH value is adjusted with watery hydrochloric acid or weak aqua ammonia
For 5.0,20 mg P-IIP and P-NIP are separately added into.Test fluid is placed in 25 °C of water-bath and stands 12 h.It is then centrifuged for point
From obtaining CoII not to be adsorbed in supernatant liquor, supernatant liquor) and other competitive Adsorption ion M () concentration surveyed with ICP
It is fixed, adsorption capacity is calculated according to result.As a result show that 20 mg P-IIP show good recognition performance to Co (II), its
Middle Co (II) relative to competitive Adsorption ion Cu ()、Ni()、Pb()、Cd() selectivity factor be respectively 4.61,
8.02,13.18 and 6.94, rather than trace adsorbent P-NIP shows very poor adsorptive selectivity to Co (II).
Embodiment 3：
(1) host material Silica preparation
In single-necked flask, 6 mL water, 15 mL ammoniacal liquor are separately added into（28%）, in 90 mL absolute ethyl alcohols, sealing magnetic is stirred
Mix 10 min.Then 9 mL TEOS are taken to be placed in the beaker containing 60 mL absolute ethyl alcohols.When well mixed after, this mixed liquor is small
The heart is rapidly added in single-necked flask, and sealing continues to stir 24 h at room temperature.After reaction terminates, centrifuge, and use second alcohol and water
Washing is several times until solution is placed in vacuum drying chamber in neutrality, and 50 °C are dried in vacuo 24 h dry for standby.
(2) silica surface modified by vinyl (Silica-APTS-AC)
The Silica 0.4g prepared in step (1) are placed in round-bottomed flask, 50 mL concentration of addition are 3 mol L-1Salt
Acid, flow back 24 h, then filters, with secondary deionized water cyclic washing to neutrality, and 80 °C are dried in vacuo taking-up after 12 h.
Then Silica 0.2g and 4 mL 3- aminopropyl triethoxysilanes (APTS) after activation is taken to be placed in 50 mL's
In dry toluene, flow back 24h, after reaction terminates, is washed respectively three times with toluene and ethanol, then be dispersed in the anhydrous of 50mL again
It is standby in toluene.
The toluene liquid that Silica disperses again after being modified containing above-mentioned coupling agent is placed in flask with three necks,round bottom, and is added
4.0 g Anhydrous potassium carbonates, ultrasonic 30min.Then 1h is stirred in ice bath, treats that temperature is down to zero, using constant pressure funnel dropwise
Add after 5 mL acrylic acid (AC), completion of dropping, nitrogen protection continues to react 12h at room temperature, that is, obtains Silica-APTS-
AC.After reaction terminates, washed successively with dry toluene and absolute ethyl alcohol three times, take out standby after 50 °C of 24 h of vacuum drying.
(3) room temperature is ultraviolet triggers polymerization synthesis ion imprinted polymer（P-IIP）
Silica-APTS-AC in step (2) is taken into 0.1 g, and 29.2 mg cabaltous nitrate hexahydrates (Co (II)), 42.6
Mg AM, 154.0 mg MBA, 10 mg BP mixing are added into the mixed solution of 40mL methanol-waters, wherein controlling
Silica-APTS-AC mass fraction is 0.294 %, and cobalt ions Co (II) concentration is for 2.5 mmol L-1, AM concentration
15 mmol L-1, MBA concentration is 25 mmol L-1, BP concentration is 1.372 mmol L-1, the volume ratio of methanol and water
For 3:1.After 30 min of ultrasound, and sealed after nitrogen deoxygenation 20min, be placed in the photochemical reaction instrument containing magnetic agitation, it is ultraviolet
Lamp is high-pressure sodium lamp of the main crest section in 365nm, and instrument controlling temperature is 25 °C.It is passed through recirculation water, illumination 8h.After reaction successively
Washed five times with methanol and deionized water difference are each, to remove the template ion of unreacted monomer and crosslinking agent and non-trace
(Co (II)), is dried in vacuo under 50 °C, then with the mol L of 2000 mL 2-1Hydrochloric acid solution washes away template ion, and spends
Ion is washed to neutrality, then vacuum drying obtains surface ion imprinted polymer (P-IIP) under 50 °C.
(4) adsorption test
It is respectively 1,3,5,10,15,20,30,50,100,150,200,250,300 and 400 to take 25 mL initial concentrations
Mg/L Co (II) solution is added in 25 mL colorimetric cylinders, is 5.0 with watery hydrochloric acid or weak aqua ammonia regulation pH value, is separately added into 10
Three groups of test fluids, are individually placed to 25, stood after 12 h in 35,45 °C of water-bath, centrifugation point by mg traces and non-trace adsorbent
From obtaining Co (II) concentration Atomic Absorption Spectrometry not to be adsorbed in supernatant liquor, supernatant liquor, and according to result meter
Calculate adsorption capacity.As a result it is 104.78 mg/g to show saturated extent of adsorption of the P-IIPs under 25 °C, is almost four times in non-trace
26.06 mg/g of adsorbent.
(5) selectivity experiment
Co() and Cu ()、Ni()、Pb()、Cd() mixing binary system competitive Adsorption, take 25 mL configure
Good concentration for 5 mg/L Co ()/M() mixed solution is added in colorimetric cylinder, and pH value is adjusted with watery hydrochloric acid or weak aqua ammonia
For 5.0,20 mg P-IIP and P-NIP are separately added into.Test fluid is placed in 25 °C of water-bath and stands 12 h.It is then centrifuged for point
From obtaining CoII not to be adsorbed in supernatant liquor, supernatant liquor) and other competitive Adsorption ion M () concentration surveyed with ICP
It is fixed, adsorption capacity is calculated according to result.As a result show that 20 mg P-IIP show good recognition performance to Co (II), its
Middle Co (II) relative to competitive Adsorption ion Cu ()、Ni()、Pb()、Cd() selectivity factor be respectively 4.42,
7.84,12.32 and 6.68, rather than trace adsorbent P-NIP shows very poor adsorptive selectivity to Co (II).
Fig. 1 is raw material and polymer infared spectrum in example 2, and a is Silica in figure；B is Silica-APTS；C is
Silica-APTS-AC；D is P-IIP.
It can be seen that in 1102 cm-1、798 cm-1、470cm-1Place can observe silica-base material Si-O-Si
Stretching vibration and deformation vibration absworption peak, illustrate the skeleton structure for all maintaining silica.Polymerizate is P-IIP,
1661 cm-1With 1530 cm-1It is the characteristic peak of amido link in polymer, it was demonstrated that monomer and template ion success blot are in matrix
Material surface.Illustrate the successful synthesis of light-initiated ion imprinted polymer.
Fig. 2 is silica scanning electron microscope (SEM) photograph and transmission electron microscope picture in example 2, and wherein a is silica scanning electron microscope (SEM) photograph；
B is silica transmission electron microscope picture.
Fig. 3 is the intermediate ion imprinted polymer scanning electron microscope (SEM) photograph of example 2 and transmission electron microscope picture, and wherein a polymerize for ion blotting
Thing scanning electron microscope (SEM) photograph；B is ion imprinted polymer transmission electron microscope picture.
It can be seen that host material is uniform-spherical particle (Silica) in 2 from figure；And in figure 3, particle surface by
Cross-linking reaction and the formation of ion imprinted polymer in polymer so that host material become it is coarse, illustrate it is light-initiated from
The successful synthesis of sub- imprinted polymer.
Claims (9)
1. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer, it is characterised in that comprise the following steps：
(1) host material Silica preparation；
(2) silica surface modified by vinyl Silica-APTS-AA；
(3) room temperature is ultraviolet triggers polymerization synthesis ion imprinted polymer P-IIP：
The Silica-APTS-AC that will be obtained in step (2), cabaltous nitrate hexahydrate (II), acrylamide (AM), N, N- methylene
Bisacrylamide (MBA) and benzophenone (BP) mixing are added into the mixed solution of methanol-water, after ultrasonic 30 min, lead to nitrogen
Sealed after gas deoxygenation 20min, be placed in the photochemical reaction instrument containing magnetic agitation；It is passed through recirculation water, illumination reaction；After reaction
Washed respectively with methanol and deionized water successively, to remove unreacted AM and MBA and non-trace template ion Co (II),
Vacuum drying, then washes away template ion with hydrochloric acid solution, and is washed with deionized water to neutrality, then obtains table in lower vacuum drying
Face ion imprinted polymer P-IIP；
Step（2）Described in silica surface modified by vinyl Silica-APTS-AA concrete operations be：
The Silica prepared in step (1) is placed in round-bottomed flask, addition concentration is 3 mol L-1Hydrochloric acid, flow back 24 h, so
After filter, with secondary deionized water cyclic washing to neutrality, take out standby after 80 DEG C of 12 h of vacuum drying；
Then the Silica after activation is taken to be placed in 3- aminopropyl triethoxysilanes (APTS) in dry toluene, flow back 24h, instead
After should terminating, washed, then be dispersed in again standby in dry toluene respectively with toluene and ethanol；
Finally, it is dispersed with above-mentioned in the Silica anhydrous toluene solutions after APTS is modified, adds Anhydrous potassium carbonate, ultrasound
30min；Then 1h is stirred in ice bath, treats that temperature is down to zero, acrylic acid (AA) is added dropwise using constant pressure funnel, drips
Bi Hou, nitrogen protection continues to react 12h at room temperature, that is, obtains Silica-APTS-AA；After reaction terminates, with dry toluene and nothing
Water-ethanol is washed successively, takes out standby after 50 DEG C of 24 h of vacuum drying.
2. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 1, it is characterised in that
Step（1）Described in the host material Silica concrete operations of preparation be：
In single-necked flask, water is separately added into, concentration is 28% ammoniacal liquor and absolute ethyl alcohol, and sealing magnetic stirs 10 min；Then take
TEOS is placed in the beaker containing absolute ethyl alcohol；After well mixed, the mixed liquor in beaker is carefully rapidly added single-necked flask
In, sealing continues to stir 24 h at room temperature；After reaction terminates, centrifuge, and with ethanol and water washing several times until solution
In neutrality, it is placed in vacuum drying chamber, 50 DEG C of 24 h dry for standby of vacuum drying.
3. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 2, it is characterised in that
The water that is added in described single-necked flask, ammoniacal liquor, absolute ethyl alcohol volume ratio are 2 ~ 6：5~15 ：30~90 ；It is wherein described
Beaker in TEOS and absolute ethyl alcohol volume ratio be 3 ~ 9：20~60.
4. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 3, its feature exists
In,
Silica mass fraction is 0.20 ~ 1.0 % in wherein described round-bottomed flask；
The ratio of Silica and APTS after the activation are 1g:5-20mL；
The amount for adding Anhydrous potassium carbonate is 0.5 ~ 5.0 g；
The amount for adding acrylic acid is 0.5 ~ 5mL.
5. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 1, it is characterised in that
Step（3）Described in methanol-water mixed solution in Silica-APTS-AC mass fraction be 0.147 ~ 0.294%；Cobalt ions
Co (II) concentration is 1.25 ~ 5.00 mmol L-1；AM concentration is 7.5 ~ 30.0 mmol L-1；MBA concentration be 5.0 ~
25.0 mmol L-1；BP concentration is 0.686 ~ 1.372 mmol L-1；The mixed liquor 40mL of methanol-water, wherein methanol with
The ratio of water is 3:1.
6. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 1, it is characterised in that
Step（3）Described in photochemical reaction instrument uviol lamp be high-pressure sodium lamp of the main crest section in 365nm, instrument controlling temperature is 25
℃。
7. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 1, it is characterised in that
Step（3）Described in photochemical reaction instrument the illumination reaction time be 2 ~ 12h.
8. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 1, it is characterised in that
Step（3）Described in the hydrochloric acid solution that washes away used in template ion be that concentration is 2 mol L-1, washed with 500 ~ 2000 mL.
9. a kind of ultraviolet method for triggering polymerization to prepare ion imprinted polymer according to claim 1, it is characterised in that
The imprinted polymer prepared in the method is used for being capable of Selective Separation to Co (II).
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| CN104258826A (en) * | 2014-09-15 | 2015-01-07 | 江苏大学 | Active/controllable mesoporous material ion-surface imprinted polymer as well as preparation method and application of ion-surface imprinted polymer |
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