CN102921393B - Granular three-dimensional ordered macroporous chelating resin preparation method - Google Patents
Granular three-dimensional ordered macroporous chelating resin preparation method Download PDFInfo
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Abstract
The invention relates to a granular three-dimensional ordered macroporous chelating resin preparation method, which comprises the following steps: (1) preparing a granular silica colloidal crystal template; (2) preparing a three-dimensional ordered macroporous polymer material (3DOM); and (3) carrying out a functionalization reaction of the granular three-dimensional ordered macroporous material: adding the 80-1200 nm granular three-dimensional ordered macroporous material (3DOM) obtained from the step (2) to a reactor, carrying out evacuation, mixing a reactant and a solvent, adding an initiator, completely stirring at a temperature of 10-90 DEG C, injecting the obtained material into the reactor filled with the 3DOM, carrying out a stirring reaction for 0.5-20 hours at a temperature of 10-120 DEG C, carrying out extraction on the obtained product by using anhydrous ethanol or acetone, and carrying out vacuum drying to obtain the granular three-dimensional ordered macroporous chelating resin. The granular three-dimensional ordered macroporous chelating resin has characteristics of strong chemical resistance, excellent solvent resistance and excellent mechanical properties, wherein Hg<2+> absorption amount is 3.8 mmol/g.
Description
Technical field
Technical scheme of the present invention relates to macromolecular material, is specifically related to a kind of preparation method of the three-dimensional ordered macroporous chelating splitter for adsorption aqueous solution precious metal ion.
Background technology
Three-dimensional ordered macroporous material (Three-dimensionally Ordered Macroporous Materials, 3DOM), because distribution uniform and ordered, the aperture in its hole are large, porosity is high, and there is special photonic crystal properties and Size dependence effect, thereby at sensor (Scott R.W.J, Yang S.M., G.Chabanis, et al.Tin Dioxide Opals and Inverted Opals:Nera-Ideal Microstructures for Gas Sensors.Adv.Mater., 2001,13 (19): 1468-1472., Qian W.P., Z.Z.Gu, Fujishima A., et al., Three-Dimensionally Ordered Macroporous Polymer Materials:An Approach for Biosensor Applications.Langmuir, 2002, 18 (11): 4526-4529.), photon chip (Ozin G.A., Yang S.M, The Race for the Photonic Chip:Collidal Crystal Assembly in silicon Wafer.Adv.Funct.Mater., 2001, 11 (2): 95-104.), photon band gap (Photonic band gap, PBG) (Lopez C.Materials Aspects of Photonic Crystals.Adv.Mater.2003, 15 (20): 1679-1704), adsorbing separation (Schroden R C, Al-Daous M, Sokolov S, et al.Hybrid macropous materials for heavy metal ion adsorption.Mater Chem., 2002, 12:3261-3267., Li Hongyu, Deng Jingheng, Liao Jufang, etc. mercapto-functionalized 3DOM TiO
2-SiO
2absorbent preparation and Study on adsorption properties. Zhongshan University's journal, 2008,47 (2): 69-73., Wu Quanzhou, He Jianfeng, Li Yuguang. the preparation of three-dimensional ordered macroporous amino functional formed material and the absorption property to Cr (VI) thereof. applied chemistry, 2009,26 (3): 367-369., Yuan L X, Wang X M, Zhang X, et al.Three-dimensionally ordered macroporous cross-linked polystyrene incorporating functional group via hydrophilic spacer arm.Chinese Chemical Letters2010,21:1493-1496.) etc. field there is wide application prospect, thereby caused greatly interest of Chinese scholars, become one of focus of present material scientific research.Although the specific area of 3DOM material with respect to mesoporous, poromerics is little, yet verified, between these macropores and Kong Yukong, be interconnected and arrange orderly open-celled structure, being conducive to material enters in hole from all directions, reduce material diffusional resistance, for the diffusion of material provides optimum flow rate and higher efficiency.For example, (the Schroden R C such as Schroden, Al-Daous M, Sokolov S, et al.Hybrid macropous materials for heavy metal ion adsorption.Mater Chem., 2002,12:3261-3267.), at the hole wall of 3DOM titanium dioxide and zirconium dioxide, introduce mercapto groups, synthesized the mercapto base-metallic oxide perforated material that aperture is respectively 300nm and 480nm.Although this 3DOM material has less specific area compared with mesoporous material, but its aperture is larger, macropore is arranged in order, and between Kong Yukong, there is free window to be interconnected, thereby make the easier infiltration of solution wherein, Gu it can effectively be applied to the absorption of heavy metal ion in solution, and adsorbance is higher, it is the clean adsorbent of a kind of very promising waste water.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of new particulate three-dimensional ordered macroporous chelating resin, the method is by controlling the reaction time of functionalization, functionalization controllable reaction is carried out in hydrophobic framework outside, introduce hydrophily and there is the functional group of metal-chelating effect, because skeleton is still hydrophobic structure, make material still can keep afterwards in use the macroporous structure of three-dimensional order simultaneously.A kind of preparation method of novel three-dimensional ordered macroporous chelating resin is easily provided, has utilized colloid crystal template technology and adopt the SiO for preparing graininess form from the method for sedimentation
2template, in the method by free-radical polymerized directly at SiO
2in template, copolymerization forms a kind ofly with the active three-dimensional ordered macroporous material of functional group, and the reactive group of three-dimensional ordered macroporous material is carried out to corresponding function reaction, and preparation has the graininess three-dimensional ordered macroporous chelating resin of chelation.
Technical scheme of the present invention is:
A preparation method for graininess three-dimensional ordered macroporous chelating resin, the method comprises the following steps:
(1) preparation of particulate silica colloid crystal template
According to the difference of particle size range, take one of following methods:
Method one: average particle size range is in the preparation of the particulate silica colloid crystal template of 80nm～600nm
Utilize
-Fink-Hohn synthetic method, in reactor, add successively absolute ethyl alcohol, ammoniacal liquor, distilled water, after stirring, add rapidly ethyl orthosilicate, wherein mass ratio is ammoniacal liquor: absolute ethyl alcohol: distilled water: ethyl orthosilicate=1: 1～60: 1～5: 0.2～10, react and after 8 hours, gained suspension is transferred in beaker, treat that solvent volatilizees to the greatest extent naturally, obtain the particulate silica colloid crystal template of average grain diameter within the scope of 80nm～600nm, then by template in muffle furnace at 200～800 ℃ sintering 2～8 hours, slowly be down to room temperature, obtain the particulate silica colloid crystal template that average particle size range bonds mutually at the silicon dioxide microsphere of 80nm～600nm,
Or method two: average particle size range is in the preparation of the particulate silica colloid crystal template of 600nm～1200nm
In the device system of the silica colloidal crystal template in preparation average grain diameter within the scope of 80nm～600nm, after teos hydrolysis is complete, add again the ammoniacal liquor of the equivalent of equal in quality proportioning, absolute ethyl alcohol, distilled water and ethyl orthosilicate, repeat 1～4 time, after hydrolysis completely, suspension is transferred in beaker, treating that solvent volatilizees naturally obtains to the greatest extent granular silica colloidal crystal template, then by template in Muffle furnace at 200～800 ℃ sintering 2～8 hours, slowly be down to room temperature, obtain average particle size range at the inter-adhesive graininess colloid crystal template of the silicon dioxide microsphere of 600nm～1200nm,
(2) preparation of three-dimensional ordered macroporous polymeric material (3DOM)
By polymerization single polymerization monomer, crosslinking agent divinylbenzene dissolves with initator mix and blend in proportion, mol ratio monomer wherein: divinylbenzene=50～150: 1, initator is 0.1%～10% of monomer and crosslinking agent quality sum, mixed liquor is injected to 80nm～1200nm sintered particles shape silica colloidal crystal template immersion that also the upper step of submergence reactor obtains, then two-mouth bottle is put into insulating box, 30～40 ℃ of prepolymerizations 1～10 hour, 45～65 ℃ of polymerizations 10～50 hours, obtain the polymer/silica composite of three-dimensional order, composite surface bulk polymer is peeled off, be placed in the ultrasonic dispersion of HF, remove template, then be washed to neutrality, 40～70 ℃ of vacuum drying, obtain the three-dimensional ordered macroporous material of 80nm～1200nm new particulate,
(3) reaction kinetic of the three-dimensional ordered macroporous material of graininess
The three-dimensional ordered macroporous material of graininess (3DOM) that adds 80nm～1200nm obtained above in reactor vacuumizes at 10～90 ℃; By reactant and solvent, and add wherein initator, then after fully stirring at 10～90 ℃, be injected in the reactor that 3DOM is housed, and at 10～120 ℃ stirring reaction 0.5～20 hour, absolute ethyl alcohol or acetone extracting 10～24 hours for products therefrom, 40～70 ℃ of vacuum drying, obtain graininess three-dimensional ordered macroporous chelating resin;
Wherein mass ratio is graininess 3DOM: reactant: solvent: initator=1: 0.5～10: 1～30: 0.1～10
In above-mentioned steps (2), initator is azodiisobutyronitrile (AIBN), ABVN, AlCl
36H
2o, dibenzoyl peroxide, dilauroyl peroxide, the special butyl ester of di-isopropyl peroxydicarbonate or benzoyl peroxide formic acid.
In above-mentioned steps (2), monomer is acrylonitrile, methyl acrylate, acrylic acid or vinyl alcohol;
In above-mentioned steps (3), reactant is hydroxylamine hydrochloride, ethylenediamine, hydrazine sulfate, thiocarbamide, N, N-methylene diacrylamine (MBA), hydrazine hydrate or monoethanolamine etc.;
In above-mentioned steps (3), solvent is ethanol, methyl alcohol, alcohol-water, methanol-water, water, acetone, benzene or chlorobenzene etc.;
In above-mentioned steps (3), initator used is NaOH, potassium hydroxide or cadmium acetate etc.;
In above-mentioned steps (3), the functional group of chelation can be amidoxime group, imidazoles, thiourea group, N, N-methylene diacrylamine (MBA), acrylate, amide groups, hydrazide group, diethanol amine amido-amidino groups or amidrazone etc.
The invention has the beneficial effects as follows:
1. the present invention's three-dimensional ordered macroporous material used is polymerizable material, has the physical and chemical performance of many excellences, as strong in chemical resistance, solvent resistance is superior, mechanical performance is good etc.Electromicroscopic photograph in accompanying drawing can find out that large pore material is before and after amidoximization, the uniform and ordered between Kong Yukong, and the morphosis being interconnected is not subject to the destruction of organic solvent.
2. the present invention can prepare as required and has specific appearance form, and the polymer chelating resin that internal structure is three-dimensional ordered macroporous structure, can adapt to special separated demand, and moulding is easy, is easy to make.
The present invention by the method for radical polymerization directly at SiO
2in template, polymerization forms the three-dimensional ordered macroporous material with reactive group, makes material synthesis step more simple and convenient.And can chelating function group be incorporated into material internal in the shorter time, by controlling the reaction time, control the introduction volume of chelation group.The three-dimensional ordered macroporous crosslinked polypropylene nitrile chelating resin that can find out 200nm amidoxim prepared by the present invention by example is to Hg
2+adsorbance up to 4.2mmol/g; The three-dimensional ordered macroporous material of 500nm amidoxim is to Hg
2+adsorbance reach 3.8mmol/g.
4. the three-dimensional ordered macroporous chelating resin that prepared by the present invention can obtain having by active on polyacrylonitrile-CN base group the amidoxime group (C (NH of chelation group by amidoximation
2) NHOH), amido-amidino groups, amidrazone, imidazole group etc., and itrile group is carried out to the multiple modifications such as amination.Can also be by the reaction acquisition-COOH groups such as hydrolysis of-CN base, thus introducing other has specific functionality chelation group, as thiourea group etc.The present invention makes material itself have highdensity active group for introducing chelating function base, and formed chelation group has hydrophilicity, make whole organic material possess the performance of anti-solvent corrosion, there is again hydrophily simultaneously, in conjunction with the special morphosis of 3DOM, be conducive to metal ion to the chelating between polymer diffusion inside and functional group and metal ion simultaneously, improve the utilization rate of functional group in chelating resin, increase the adsorbance of chelating resin.From electromicroscopic photograph, can find out, three-dimensional ordered macroporous material has height homogeneous, in order and the morphosis that has " hole window " passage to interconnect; In table 1, the three-dimensional ordered macroporous crosslinked polypropylene nitrile of 200nm amidoxim is to Hg
2+adsorbance is up to 4.2mmol/g.
Accompanying drawing explanation
Fig. 1: embodiment bis-mesoporous are the electromicroscopic photograph of the three-dimensional ordered macroporous crosslinked polypropylene nitrile of 200nm material;
Fig. 2: embodiment bis-mesoporous are the photo in kind of the three-dimensional ordered macroporous crosslinked polypropylene nitrile of 200nm graininess material;
Fig. 3: embodiment bis-mesoporous are the electromicroscopic photograph of the three-dimensional ordered macroporous chelating resin after 200nm amidoxim;
Fig. 4: embodiment tri-mesoporous are the electromicroscopic photograph of the three-dimensional ordered macroporous crosslinked polypropylene nitrile of 500nm (3DOM CLPAN);
Fig. 5: embodiment tri-mesoporous are the electromicroscopic photograph of the three-dimensional ordered macroporous chelating resin after 500nm amidoxim;
Specific implementation method
Embodiment mono-:
Average grain diameter is the preparation of the 80nm graininess three-dimensional ordered macroporous chelating resin that contains amidoxime group
(1) preparation of 80nm particulate silica colloid crystal template
Under room temperature, in being furnished with the there-necked flask of electric stirring, add successively ammoniacal liquor, 10.0g deionized water that 60.4g absolute ethyl alcohol, 3.0g percent concentration are 25%, after stirring, in there-necked flask, add rapidly 8.3g ethyl orthosilicate again, react and after 8 hours, the suspension of gained is transferred in beaker, treat that solvent volatilizees to the greatest extent naturally, obtain graininess titanium dioxide template, then by template sintering 2 hours at 400 ℃ in Muffle furnace, slowly be down to room temperature, obtaining average grain diameter is the silica colloidal crystal template of 80nm.
(2) preparation of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN)
After 0.1319mol (7.01g) acrylonitrile 0.0016mol (0.21g) divinylbenzene and 0.0920g initiator A IBN fully dissolve in 50mL beaker, mixed liquor is injected in the bottle that fills sintering template, soaks template to transparent.40 ℃ of polymerizations 2 hours, polymerization is 24 hours at 50 ℃, obtains the polymer/silica composite of three-dimensional order.Composite surface bulk polymer is peeled off, be placed in the ultrasonic dispersion of HF to remove template.Then be repeatedly washed to neutrality, vacuum drying at 60 ℃ (pressure is lower than atmospheric pressure 0.1MPa, following steps and case study on implementation vacuum drying pressure with), obtains the 3DOMCLPAN that average pore size is 80nm.
(3) amidoximation of 3DOM CLPAN
Take dried 3DOM CLPAN 0.2460g and be placed in the two-mouth bottle that magneton is housed, two-mouth bottle is sealed and vacuumized; Accurately taking hydroxylamine hydrochloride 0.3791g is placed in the single port bottle of magneton to be housed and to measure methyl alcohol 2.0mL and is injected into the single port bottle that fills hydroxylamine hydrochloride it is fully dissolved; Weighing sodium hydroxide 0.2192g is dissolved in 2.0mL water; The sodium hydrate aqueous solution fully dissolving is injected in the single port bottle that fills hydroxylamine hydrochloride/methanol solution under room temperature to stirring reaction 2 hours, after standing 0.5 hour, with syringe, by supernatant liquor sucking-off, be injected in the evacuated vial that 3DOM CLPAN is housed, at 70 ℃, stirring reaction is 1 hour.Stop, after reaction, using successively distilled water, ethanol supersound washing, and with ethanol extracting 12 hours, vacuum drying at 50 ℃ afterwards, obtains the 3DOM chelating resin of amidoxim.
The mensuration of selective absorption amount:
(4) determining adsorption of metal ion
Get the novel three-dimensional ordered macroporous chelating resin containing thanking to peace oximido making in 10mg step (3) and be placed in the reaction bulb that magneton is housed, then add the Ag of 1mL0.1mol/L
+, Pt
2+, Ru (IV), Pb
2+, Hg
2+, Cu
2+metal ion solution and the buffer solution of 19mLpH=2.0, at room temperature (25 ℃) stir 24 hours, filter and take out hole material after standing 2 hours, retain filtrate.With the concentration of metal ions after titration measuring absorption, Hg
2+concentration be 3.0mmol/L, before the concentration of other metal ions and absorption, relatively change not quite, according to the variation of concentration of metal ions before and after absorption, according to following formula, calculate the adsorbance of metal ion:
Q＝(C
1-C
2)×V/m
In formula, Q-adsorbance (mmol/g); C
1concentration of metal ions (mmol/L) before-absorption; C
2concentration of metal ions (mmol/L) after-absorption; V-liquor capacity (L); The quality (g) of m-hole material.
This chelating resin under the condition of pH=2 to Hg
2+adsorbance be 4.0mmol/g.
Embodiment bis-
Average pore size is the preparation of the 200nm graininess three-dimensional ordered macroporous chelating resin that contains amidoxime group
(1) preparation of 200nm particulate silica colloid crystal template
The preparation process of 200nm particulate silica colloid crystal template is with reference to embodiment mono-step (1), only adjust reagent dosage: absolute ethyl alcohol 75.5g, percent concentration is 25% ammoniacal liquor 4.2g, deionized water 8.5g, ethyl orthosilicate 15.1g obtains the silica colloidal crystal template that average grain diameter is 200nm.
(2) preparation of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) is with reference to embodiment mono-step (2)
Fig. 1 obtains with the three-dimensional ordered macroporous crosslinked polypropylene nitrile of electron scanning electron-microscope scanning 200nm (3DOM CLPAN) that model is Hitachi S-4300,3DOM CLPAN shows the macroporous structure of three-dimensional order as seen from the figure, and presents the pore passage structure that is interconnected between macropore and macropore.
Fig. 2 is the photo in kind of 200nm graininess 3DOM CLPAN material.
(3) amidoximation of 3DOM CLPAN is with reference to example one step (3).
Hg
2+the mensuration of adsorbance is with reference to embodiment mono-step (4)
This chelating resin under the condition of pH=2.0 to Hg
2+adsorbance be 4.2mmol/g.
Fig. 3 obtains with the 3DOM CLPAN that model is the electron scanning electron-microscope scanning amidoxim of Hitachi S-4300.By photo, found out, 3DOM CLPAN is after amidoximation, after itrile group is converted into amidoxime group, its original ordered big hole structure is not destroyed, and material still presents aperture uniform and ordered, the morphosis being interconnected between macropore.This open-celled structure plays the effect of mass transfer passage in the process of adsorbing metal ions, is conducive to improve adsorbance.
Embodiment tri-
Average grain diameter is the preparation of the 500nm graininess three-dimensional ordered macroporous chelating resin that contains amidoxime group
(1) preparation of particulate silica colloid crystal template
The preparation process of particulate silica template is with reference to example one step (1), only adjust the addition of reagent: absolute ethyl alcohol 90g, percent concentration is 25% ammoniacal liquor 8.2g, deionized water 11.5g, ethyl orthosilicate 16.1g obtains the silica colloidal crystal template that average grain diameter is 500nm.
(2) preparation of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) is with reference to embodiment mono-step (2).
(3) amidoximation of three-dimensional ordered macroporous crosslinked polypropylene nitrile is with reference to embodiment mono-step (3).
(4) Hg
2+determining adsorption with reference to embodiment mono-step (4), this resin under the condition of pH=2.0 to Hg
2+adsorbance is 3.8mmol/g.
The electromicroscopic photograph of the three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) that Fig. 4 is is 500nm with the electron scanning electron-microscope scanning aperture that model is Hitachi S-4300;
The three-dimensional ordered macroporous chelating resin of the amidoxim that Fig. 5 is is 500nm with the electron scanning electron-microscope scanning aperture that model is Hitachi S-4300 obtains.By photo, found out, 3DOM CLPAN is after amidoximation, and after itrile group is converted into amidoxime group, its original ordered big hole structure is not destroyed, and material still presents aperture uniform and ordered, the morphosis being interconnected between macropore.This open-celled structure plays the effect of mass transfer passage in the process of adsorbing metal ions, is conducive to improve adsorbance.
Embodiment tetra-
Average grain diameter is the preparation of the three-dimensional ordered macroporous chelating resin that contains amidoxime group of 800nm
(1) preparation process of the particulate silica colloid crystal template that average grain diameter is 800nm is with reference to embodiment bis-steps (1), data are constant, then at interval of 8 hours, add ammoniacal liquor, absolute ethyl alcohol, distilled water and the ethyl orthosilicate of the equivalent of equal in quality proportioning, add three times.
(2) preparation of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) is with reference to embodiment mono-step (2).
(3) amidoximation of three-dimensional ordered macroporous crosslinked polypropylene nitrile is with reference to embodiment bis-steps (3).
(4) Hg
2+determining adsorption is with reference to embodiment mono-step (4), this resin under the condition of pH=2.0 to Hg
2+adsorbance reaches 3.2mmol/g.
Embodiment five
Average grain diameter is the preparation of the graininess 3DOM chelating resin that contains amino-amidino groups of 200nm
(1) preparation process of the particulate silica colloid crystal template that average grain diameter is 200nm is with reference to example two steps (1).
(2) preparation process of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) is with reference to example one step (2).
(3) preparation of the three-dimensional ordered macroporous chelating resin that contains amino-amidino groups group
Take dried 3DOM CLPAN 0.2140g, the hole material weighing up is put in two mouthfuls of reaction bulbs that magneton is housed, and vacuumizes.Separately get a single port reaction bulb that magneton is housed, in bottle, add AlCl
36H
2o 0.0106g, is injected into 1.5245g ethylenediamine (EDA) to fill AlCl
36H
2in the reaction bulb of O, magnetic agitation is injected into after fully dissolving in two mouthfuls of reaction bulbs that hole material is housed, and at 110 ℃, stirring reaction is 3 hours.Deionized water, the ethanol for material of gained are fully washed, and with ethanol extracting 12 hours to then vacuum drying 24 hours at 50 ℃.The graininess 3DOM chelating resin that both must contain amino-amidino groups.
(4) the 3DOM chelating resin that gained contains amino-amidino groups to the absorption of each metal ion species is sequentially:
Cu
2+＞Ag
+＞Zn
2+＞Ni
2+＞Pb
2+。
Embodiment six
Average grain diameter is the preparation of the three-dimensional ordered macroporous chelating resin that contains amidrazone group of 200nm
(1) preparation process of the particulate silica colloid crystal template that average grain diameter is 200nm is with reference to example two steps (1).
(2) preparation process of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) is with reference to example one step (2).
(3) preparation of the three-dimensional ordered macroporous chelating resin that contains amidrazone group
Take dried 3DOM CLPAN 0.05g and pack in two mouthfuls of reaction bulbs with magneton, and vacuumize discharge air.Get a single port reaction bulb and take hydrazine sulfate 0.24g and pack in single port reaction bulb, measure ethanol 2mL and be injected in single port reaction bulb, magnetic agitation is dissolved in ethanol hydrazine sulfate; Separately get a single port reaction bulb, weighing sodium hydroxide 0.07g is dissolved in 1mL water, and aqueous sodium hydroxide is joined to hydrazine sulfate in the mixed liquor of ethanol, and magnetic agitation is fully reacted it; The supernatant liquor sucking-off of gained after reaction is injected in the reaction bulb that 3DOM CLPAN is housed, and normal temperature lower magnetic force stirs 1h, makes solution enter into fully material internal.Then the oil bath that two mouthfuls of reaction bulbs is placed in to 75 ℃ is reacted 2 hours, take out material and fully wash with ethanol, and with ethanol extracting after 12 hours in 60 ℃ of vacuum drying.The three-dimensional ordered macroporous chelating resin that must contain amidrazone group.
(5) to Hg
2+absorption with reference to embodiment mono-step (4), the three-dimensional ordered macroporous chelating resin that gained contains amidrazone group is to Hg
2+adsorption rate up to 80%.
Embodiment seven
Average grain diameter is the preparation of the graininess three-dimensional ordered macroporous chelating resin that contains imidazole group of 200nm
(1) preparation process of the particulate silica colloid crystal template that average grain diameter is 200nm is with reference to example two steps (1).
(2) preparation process of three-dimensional ordered macroporous crosslinked polypropylene nitrile (3DOM CLPAN) is with reference to example one step (2).
(3) preparation of the three-dimensional ordered macroporous chelating resin that contains imidazole group
Take dried 3DOM CLPAN 0.05g and be loaded in two mouthfuls of reaction bulbs, and reaction bulb is vacuumized to discharge air; Separately get a single port reaction bulb, taking cadmium acetate 0.01g packs in single port reaction bulb and preserves at ar gas environment lower seal, measure monoethanolamine 2mL and be injected in single port reaction bulb, inject at room temperature magnetic agitation 0.5 hour of chlorobenzene 8mL simultaneously, make monoethanolamine and cadmium acetate fully be dissolved in chlorobenzene; Mixed liquor after dissolving is injected in two mouthfuls of reaction bulbs that 3DOM CLPAN is housed, and room temperature lower magnetic force stirs 0.5 hour; Then, reaction bulb is placed under the oil bath magnetic agitation of 120 ℃ and reacts 2 hours, takes out material and fully washs with ethanol, and with ethanol extracting vacuum drying 24 hours at 60 ℃ after 12 hours, must contain the three-dimensional ordered macroporous chelating resin of imidazole group.
(4) resulting materials under the condition of pH=5 to Cu
2+there is good adsorptive selectivity; When pH=4 to Pb
2+there is good adsorptive selectivity; When pH=2 to Cr
6+there is good adsorption effect.
By the amidoximation to three-dimensional ordered macroporous crosslinked polypropylene nitrile, the three-dimensional ordered macroporous crosslinked polypropylene nitrile that is 200nm to aperture is 70 ℃ of amidoximations 1 hour, and resulting materials is at 25 ℃, pH=2, initial concentration C
0under the condition of=5.0mmol/L to Hg
2+carry out adsorption experiment, adopt the method for EDTA titration, take xylenol orange as indicator, record it to Hg
2+adsorbance up to 4.2mmol/g.Far above other sorptive materials to Hg
2+adsorbance.
Embodiment eight
Average grain diameter is the preparation of the graininess three-dimensional ordered macroporous chelating resin that contains thiourea group of 200nm
(1) preparation of the particulate silica colloid crystal template that average grain diameter is 200nm is with reference to example two steps (1);
(2) preparation of the three-dimensional ordered macroporous crosslinked polypropylene nitrile of graininess (3DOM CLPAN) is with reference to example one step (2);
(3) preparation of the graininess three-dimensional ordered macroporous chelating resin that contains thiourea group
Get 0.0431g hole material 3DOM-1 and be placed in the reactor with magneton, and vacuumize; 0.1051g thiocarbamide is dissolved in 2mL aniline, and under room temperature, stir 1 hour, the solution mixing is injected in the reactor that material is housed, room temperature lower magnetic force stirs 2 hours, rising temperature to 60 ℃ reaction 10 hours, fully washs distilled water, ethanol for resulting materials, and with ethanol drawer 12 hours, in vacuum drying oven, 50 ℃ are dried 24 hours, both must contain the graininess three-dimensional ordered macroporous chelating resin of thiourea group.
Its mesopore material 3DOM-1 is obtained by following step:
Take the 3DOM CLPAN 0.0484g obtaining in step (2) and be loaded in the reactor with magneton, and vacuumize, 0.3g ethylene glycol is mixed with 0.05g NaOH and 2mL hydrogen peroxide, and stir 1 hour under room temperature; The solution mixing is injected in the reactor that 3DOM CLPAN is housed, room temperature magnetic agitation 2 hours, rising temperature to 50 ℃ reaction 5 hours.Reacted material is fully washed with distilled water, and in vacuum drying oven 60 ℃ dry 24 hours;
Getting the dried material 0.0450g that step obtains is loaded in the reactor with magneton, and vacuumize, in container, add 2ml benzene, room temperature lower magnetic force stirs 2 hours, reactor is transferred to and in ice-water bath, adds 0.5mL thionyl chloride, and fully stir 0.5 hour, rising temperature to 60 ℃ reaction 7 hours, take out material and fully wash with hydrochloric acid, distilled water, the ethanol of 0.5mol/L, and with ethanol extracting after 12 hours in vacuum drying oven 50 ℃ be dried 24 hours; Both obtained hole material 3DOM-1;
Embodiment nine
Average grain diameter is the N of 500nm, the preparation of N-methylene diacrylamine polyacrylic based graininess three-dimensional ordered macroporous chelating resin
(1) preparation of the particulate silica colloid crystal template that average grain diameter is 500nm is with reference to example three steps (1);
(2) preparation of the three-dimensional ordered macroporous cross linked polyacrylate of graininess (3DOM CLPAA) is with reference to example one step (2); Only changing monomer is acrylic acid (AA);
(3) average grain diameter is 500nm contains N, the preparation of the graininess three-dimensional ordered macroporous chelating resin of N-methylene diacrylamine;
Get the three-dimensional ordered macroporous polyacrylic acid material 0.0482g of dry graininess and be placed in reactor, and vacuumize.By 0.2011g N, N-methylene diacrylamine (MBA), 0.02g AIBN are injected into after mixing with 2mL ethanol and are equipped with in 3DOMCLPAA material reactor, room temperature lower magnetic force stirs 2 hours, be warming up to 50 ℃ of reactions 10 hours, reacted material is fully washed with cold and hot distilled water, after 50 ℃ of vacuum drying 24 hours in vacuum drying oven, both must contain N, N-methylene and the graininess three-dimensional ordered macroporous chelating resin of acrylamide.
Embodiment ten
Average grain diameter is the preparation of the graininess three-dimensional ordered macroporous chelating resin containing diethanol amine of 800nm
(1) preparation of the particulate silica colloid crystal template that average grain diameter is 800nm is with reference to embodiment tetra-steps (1);
(2) preparation of the three-dimensional ordered macroporous polyvinyl alcohol material of graininess that average grain diameter is 800nm
By in particulate silica colloid crystal template dress obtained above and reactor, and vacuumize; Get under vinyl alcohol monomer 8.05g and divinylbenzene 0.4g and 0.05g dibenzoyl peroxide (BPO) room temperature and stir, BPO is dissolved completely, the solution mixing is injected in the reactor that particulate silica colloid crystal template is housed, make template completely by solution submergence, under room temperature, soak 2 hours, 40 ℃ of pre-polymerizations 2 hours, 50 ℃ of polymerizations 24 hours, obtain polyvinyl alcohol/earth silicon material; Resulting materials ultrasonic dispersion in HF, to take out template, and is washed with water to neutrality, and in vacuum drying oven, 60 ℃ of vacuum drying of vacuum are 24 hours, both the three-dimensional ordered macroporous polyvinyl alcohol material of graininess;
(3) preparation of the graininess three-dimensional ordered macroporous chelating resin that contains diethanol amido
Take hole material 3DOM-20.04506g and be placed in reactor, and vacuumize; 0.7mL diethanol amine is dissolved in 3mL ethanol, the solution mixing is injected in the reactor that material is housed, and stir 2 hours in room temperature lower magnetic force, in reactor, inject 0.5mL THF, rising temperature to 35 ℃ reaction 10 hours, resulting materials after reaction is fully washed with NaOH, distilled water, the ethanol of 0.1mol/L, and with ethanol extracting after 12 hours, in 50 ℃ of vacuum drying 24 hours; The graininess three-dimensional ordered macroporous chelating resin that both must contain diethanol amine group;
Wherein 3DOM-2 is obtained by following reactions steps:
Take in step (2) and obtain the three-dimensional ordered macroporous polyvinyl alcohol material 0.0501g of graininess, be placed in reactor, and vacuumize; 2mL benzene and 0.2mL pyridine are mixed after all having and be injected in reactor, make the complete submergence material of liquid level, in room temperature lower magnetic force, stir 2 hours; Reactor is moved on in ice-water bath, under condition of ice bath, add thionyl chloride 0.45mL, and fully stir 0.5 hour in frozen water territory, then reactor is warming up to 60 ℃ of reactions 7 hours, resulting materials is fully washed with hydrochloric acid, the ethanol of 0.1mol/L, and with ethanol extracting 12 hours, under 50 ℃ of conditions, vacuum drying was 24 hours;
(4) resulting materials under the condition of pH=3 to Cu
2+there is good adsorption effect.
Embodiment 11
Average grain diameter is the preparation of the 200nm three-dimensional ordered macroporous crosslinked polyacrylate base of the graininess chelating resin that contains amide group
(1) preparation process of the particulate silica colloid crystal template that average grain diameter is 200nm is with reference to embodiment bis-steps (1);
(2) preparation of the three-dimensional ordered macroporous crosslinked polyacrylate of graininess (3DOM CLPMA) that average grain diameter is 200nm
Get the 200nm silica colloidal crystal template making in above-mentioned steps and be loaded in reactor, and vacuumize; 5mL (55.51mmol) methyl acrylate is mixed with 0.12mL (0.86mmol) divinylbenzene, and add 0.05g azodiisobutyronitrile (AIBN) in mixed liquor, room temperature lower magnetic force stirs, and makes AIBN be dissolved in mixed liquor completely; The solution preparing is injected in the reactor that template is housed, make the complete submergence template of liquid level, and fully soak 2 hours under room temperature, reactor is placed under 40 ℃ of conditions to prepolymerization reaction 2 hours, rising temperature to 50 ℃ reaction 24 hours, reacted material is placed in to the ultrasonic dispersion of HF, to remove silica template, and be washed with distilled water to neutrality, 60 ℃ of vacuum drying 24 hours, both the average grain diameter three-dimensional ordered macroporous cross linked polyacrylate methyl esters of the graininess material (3DOM CLPMA) that is 200nm;
(3) preparation of the three-dimensional ordered macroporous chelating resin that contains amide group
Get the 3DOM CLPMA 0.0504g obtaining in above-mentioned steps and be placed in the reactor with magneton, and vacuumize; Measuring ethylenediamine 0.56mL (0.5g) is dissolved in magnetic agitation in 2mL acetone and after it is mixed, is injected in the reactor that material is housed, under room temperature, stir 1 hour, rising temperature to 90 ℃ reaction 8 hours, products therefrom is fully washed with distilled water and acetone, and with acetone extracting vacuum drying 24 hours at 50 ℃ after 12 hours, both must contain the three-dimensional ordered macroporous chelating resin of amide group.
Embodiment 12
Average grain diameter is the preparation of the three-dimensional ordered macroporous PMA base of the graininess that the contains hydrazides group chelating resin of 200nm
(1) preparation process of the silica colloidal crystal template that average grain diameter is 200nm is with reference to embodiment bis-steps (1);
(2) preparation of the three-dimensional ordered macroporous cross linked polyacrylate methyl esters (3DOM CLPMA) that average grain diameter is 200nm is with reference to embodiment 11 steps (2);
(3) preparation of the graininess three-dimensional ordered macroporous chelating resin that contains hydrazides group
Get the 3DOM CLPMA 0.0513g obtaining in above-mentioned steps and be placed in the reactor with magneton, and vacuumize; 0.5mL (hydrazine hydrate) is dissolved in to room temperature lower magnetic force in 2mL acetone and stirs 1 hour, the solution mixing is injected in the reactor that hole material is housed, room temperature lower magnetic force stirs 2 hours, rising temperature to 90 ℃ reaction 10 hours; Products therefrom is fully washed with distilled water and acetone, then use acetone extracting 12 hours, in 50 degrees Celsius of vacuum drying 24 hours; Both must contain the three-dimensional ordered macroporous chelating resin of hydrazides group.
Claims (4)
1. a preparation method for graininess three-dimensional ordered macroporous chelating resin, is characterized by and comprise the following steps:
(1) preparation of particulate silica colloid crystal template
According to the difference of particle size range, take one of following methods:
Method one: average particle size range is in the preparation of the particulate silica colloid crystal template of 80nm～600nm
Utilize
-Fink-Hohn synthetic method, in reactor, add successively absolute ethyl alcohol, ammoniacal liquor, distilled water, after stirring, add rapidly ethyl orthosilicate, wherein mass ratio is ammoniacal liquor: absolute ethyl alcohol: distilled water: ethyl orthosilicate=1:1～60:1～5:0.2～10, react and after 8 hours, gained suspension is transferred in beaker, treat that solvent volatilizees to the greatest extent naturally, obtain the particulate silica colloid crystal template of average grain diameter within the scope of 80nm～600nm, then by template in muffle furnace at 200～800 ℃ sintering 2～8 hours, slowly be down to room temperature, obtain the particulate silica colloid crystal template that average particle size range bonds mutually at the silicon dioxide microsphere of 80nm～600nm,
Or method two: average particle size range is in the preparation of the particulate silica colloid crystal template of 600nm～1200nm
In the device system of the silica colloidal crystal template in preparation average grain diameter within the scope of 80nm～600nm, after teos hydrolysis is complete, add again the ammoniacal liquor of the equivalent of equal in quality proportioning, absolute ethyl alcohol, distilled water and ethyl orthosilicate, repeat 1～4 time, after hydrolysis completely, suspension is transferred in beaker, treating that solvent volatilizees naturally obtains to the greatest extent granular silica colloidal crystal template, then by template in Muffle furnace at 200～800 ℃ sintering 2～8 hours, slowly be down to room temperature, obtain average particle size range at the inter-adhesive graininess colloid crystal template of the silicon dioxide microsphere of 600nm～1200nm,
(2) preparation of three-dimensional ordered macroporous polymeric material (3DOM)
By polymerization single polymerization monomer, crosslinking agent divinylbenzene dissolves with initator mix and blend in proportion, mol ratio monomer: divinylbenzene=50～150:1 wherein, initator is 0.1%～10% of monomer and crosslinking agent quality sum, mixed liquor is injected to 80nm～1200nm sintered particles shape silica colloidal crystal template immersion that also the upper step of submergence reactor obtains, then two-mouth bottle is put into insulating box, 30～40 ℃ of prepolymerizations 1～10 hour, 45～65 ℃ of polymerizations 10～50 hours, obtain the polymer/silica composite of three-dimensional order, composite surface bulk polymer is peeled off, be placed in the ultrasonic dispersion of HF, remove template, then be washed to neutrality, 40～70 ℃ of vacuum drying, obtain the three-dimensional ordered macroporous material of 80nm～1200nm graininess, (3) reaction kinetic of the three-dimensional ordered macroporous material of graininess
The three-dimensional ordered macroporous material of graininess (3DOM) that adds 80nm～1200nm obtained above in reactor vacuumizes at 10～90 ℃; By reactant and solvent, and add wherein initator, then after fully stirring at 10～90 ℃, be injected in the reactor that 3DOM is housed, and at 10～120 ℃ stirring reaction 0.5～20 hour, absolute ethyl alcohol or acetone extracting 10～24 hours for products therefrom, 40～70 ℃ of vacuum drying, obtain graininess three-dimensional ordered macroporous chelating resin;
Wherein mass ratio is graininess 3DOM: reactant: solvent: initator=1:0.5～10:1～30:0.1～10;
In described step (2), monomer is acrylonitrile, methyl acrylate, acrylic acid or vinyl alcohol;
In described step (3), reactant is hydroxylamine hydrochloride, ethylenediamine, hydrazine sulfate, thiocarbamide, N, N-methylene diacrylamine (MBA), hydrazine hydrate or monoethanolamine;
In described step (3), the functional group of chelation can be amidoxime group, imidazoles, thiourea group, N, N-methylene diacrylamine (MBA), acrylate, amide groups, hydrazide group, diethanol amine amido-amidino groups or amidrazone.
2. the preparation method of graininess three-dimensional ordered macroporous chelating resin as claimed in claim 1, it is characterized by initator in step (2) is azodiisobutyronitrile (AIBN), ABVN, AlCl
36H
2o, dibenzoyl peroxide, dilauroyl peroxide, the special butyl ester of di-isopropyl peroxydicarbonate or benzoyl peroxide formic acid.
3. the preparation method of graininess three-dimensional ordered macroporous chelating resin as claimed in claim 1, it is characterized by solvent in step (3) is ethanol, methyl alcohol, alcohol-water, methanol-water, water, acetone, benzene or chlorobenzene.
4. the preparation method of graininess three-dimensional ordered macroporous chelating resin as claimed in claim 1, it is characterized by initator used in step (3) is NaOH, potassium hydroxide or cadmium acetate.
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| 接枝型偕胺肟树脂/SiO2功能复合微粒的制备;高学超等;《应用化学》;20100331;第27卷(第3期);313-317 * |
| 高学超等.接枝型偕胺肟树脂/SiO2功能复合微粒的制备.《应用化学》.2010,第27卷(第3期),313-317. |
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