CN104841385B - The mesh structural porous heavy-metal adsorption material and preparation method of load nano-sized iron oxide - Google Patents
The mesh structural porous heavy-metal adsorption material and preparation method of load nano-sized iron oxide Download PDFInfo
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- CN104841385B CN104841385B CN201410781433.5A CN201410781433A CN104841385B CN 104841385 B CN104841385 B CN 104841385B CN 201410781433 A CN201410781433 A CN 201410781433A CN 104841385 B CN104841385 B CN 104841385B
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Abstract
The invention discloses the mesh structural porous heavy-metal adsorption material and preparation method of a kind of load nano-sized iron oxide.First with diallylamine and 2-chloroethyl alcohol as raw material, water be solvent synthesis diallyl ethylol amine, it is then quaternized with end position dibromoalkane, prepare double (bromination diallyl ethoxy alkylammonium) monomers；Then free yl solution polymerization mode synthetic mesh porous material is adopted, then is immersed in iron salt solutions, the hydroxyl-oxygen complex of the hydrolysis fabricated in situ Fe by controlling Fe (III), then be transformed into ferrum oxide and loaded on porous material.The adsorbing material of the present invention has larger and regular pore passage structure, and good to waste water permeability, treatment effeciency is higher；Nano-sized iron oxide with higher stability and dispersibility so as to higher adsorption surface area, improve adsorption effect；Product of the present invention have the advantages that zeolite regeneration excellent performance, heavy metal be easily recycled, service life cycle it is long, be adapted to various heavy metal wastewater therebies process.
Description
Technical field
The invention belongs to heavy metal-polluted water treatment field, a more particularly to a kind of mesh structural porous huge sum of money for load nano-sized iron oxide
Category adsorbing material and preparation method.
Background technology
Heavy metal is one of environmental pollution most serious, the pollution of harm maximum healthy to people.With other pollutions
Thing compares, and heavy metal pollution has the characteristics that：(1) it is micro to produce notable poisonous effect；(2) can not be dropped by microorganism
Solution；(3) can be enriched with higher biological internal thousands of Radix Achyranthis Bidentatae after being absorbed by organism, and with biopolymer (such as
Protein, enzyme etc.) there is strong interaction and make them lose activity；(4) cumulative bad is caused during some organs can be accumulated in
Poisoning.Due to heavy metal to surrounding medium pollution with disguised, chronicity and cumulative feature, difficulty of governance is very big,
It is the difficult problem in current International Environmental Protection field, and whole world environmental protection sector needs the difficult problem for solving energetically in the long duration from now on.
Although have developed such as chemical precipitation method, ferrite process, oxidation-reduction method, ion exchange, evaporation for heavy metal pollution
Concentration method, enhancing ultrafiltration method, absorption method, reverse osmosiss, electroosmose process, floatation, bioanalysises, electric flocculation, electric flotation, electro-deposition etc.
Method, but lack universal effectively administering method.Compare with other methods, absorption method has advantages below：(1) as which is profit
With the affinity interaction of the high-ratio surface energy, surface active function group and heavy metal ion of porous solid material make heavy metal from
Son attachment is separated on the adsorbent material and with liquid phase main body, therefore, it is applied widely, with universality；(2) adsorption material for selecting
Material is appropriate, and the heavy metal ion in process water can be made to remove completely, the depth of low concentration wastewater and waste water is thus particularly suited for
Reason；(3) handling process is simple, and running cost is low, easy to use；(4) adsorbing material wide material sources, including natural adsorbent, conjunction
Enrich very much into the several types such as adsorbent and biological adsorption agent, the especially species of natural adsorbent；(5) processing cost compared with
It is low, easily received by vast contaminating enterprises.
Absorption method is applied to the performance that it is critical only that adsorbing material of heavy metal containing wastewater treatment.Natural adsorbing material, it is such as swollen
Profit soil, zeolite, Kaolin, meerschaum, Paligorskite, kieselguhr, the wood fiber, corn stalk, rice husk, wood flour, bark, shitosan and corruption
Phytic acid class adsorbent etc., as the defect on this body structure, the adsorption capacity of heavy metal ion are less, selectivity is low, regeneration
Difficulty, is also easy to produce a large amount of garbages containing heavy metal and causes secondary pollution.Synthesis adsorbing material is mainly gathered by vinyl monomer
Close and be obtained, the adsorbing material of different structure is obtained by changing monomer composition and polymerization methodses, in addition, can also pass through chemical reaction
Further functionalization gives adsorbing material special performance, such as with tapioca as raw material, prepares starch by emulsion polymerization
With glycidyl methacrylate (GMA) graft copolymer (Lin Meiying, Shang little Qin, Li Shuyan, etc. amino modified starch weight
The preparation and application of metallic wastewater inorganic agent. chemical industry is in progress, and 2011,30 (4)：854-856.), in the N of aminomethyl polystyrene
2 carboxymethyls are connected on atom and makes chelating resin ((Liu F Q, Li L J, Ling P P, Jing X S, Li C H, Li A
M,You X Z.Interaction mechanism of aqueous heavy metals onto a newly-
synthesized IDA-chelating resin:isotherms,thermodynamics and kinetics.Chem
Eng J,2011,173(1):106-114)), on guar gum graft polypropylene acetoacetic ester (Singh V, Sharma A K,
Maurya S.Efficient Cadmium(II)Removal from Aqueous Solution Using Microwave
Synthesized Guar Gum-Graft-Poly(ethylacrylate).Ind Eng Chem Res,2009,48(10):
4688-4696.) etc..These synthesis adsorbing materials often have that manufacturing cost is higher, and adsorption capacity is limited, suitable to actual waste water
Should be able to power it is poor, it is difficult to the problems such as reaching intended effect.Then generally existing microorganism heavy metal has choosing to biological adsorption agent
Selecting property, it is difficult to find a kind of microorganism pervasive to contents of many kinds of heavy metal ion, and strain improvement than it is relatively time-consuming the problems such as, rarely have
Successful example in actual heavy metal containing wastewater treatment.How according to absorption principle and its feature, and heavy metal ion and a huge sum of money
It is the key for improving heavy metal ion adsorbed treatment effect that the characteristics of category waste water researches and develops new and effective adsorbing material.
The content of the invention
For the problem existed for heavy metal ion adsorbing material, an object of the present invention is to provide a kind of high score
Sub- reticulated porous materials, are characterized in：(1) with larger and more regular mesh, pass through from duct beneficial to waste water is processed, because
This, has higher permeability to processing waste water, improves the efficiency of wastewater treatment；(2) at the node of mesh and on hole wall both
The abundant positive charge of distribution, and with abundant-OH, improve the adsorption of heavy metal ion；(3) adopt fabricated in situ
The modified oxide of Fe (III) on porous material, is made the active group-OH on porous material participate directly in Fe by mode
(III) stability and dispersibility of the oxide of the Fe (III) of load in the structure of oxide, are improve；(4) load Fe
(III) after oxide, higher permeability had both been kept, and had improve specific surface area again, improve absorbability.
The mesh structural porous heavy-metal adsorption material of the load nano-sized iron oxide of the present invention, is that yellow is loose to light brown fragility
Reticulated porous materials, its structural formula is as shown in formula I：
In formula I, n is 4～6 integer.
Second object of the present invention is the mesh structural porous heavy metal adsorption material of the load nano-sized iron oxide for providing above-mentioned
The preparation method of material, it comprises the steps：
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 1.5～3.0: 1: 1～1.05 dispensing in molar ratio, first by diene
Propyl group amine and its isopyknic water are added in reactor, add the solid carbonic acid potassium of potassium carbonate total amount 1/3, it is warming up to 60～
75 DEG C, Deca 2-chloroethyl alcohol, time for adding control in 3 hours, the saturated solution that then Deca is made into by remaining potassium carbonate, Deca
Time control continued reaction 1～2 hour in 2 hours；It is transferred in separatory funnel, stands 30min, point liquid, oil phase is with anhydrous
Potassium carbonate is dried, and steams unreacted diallylamine and reacts into next round, and vacuum distillation obtains diallyl ethylol amine；
(2) diallyl ethylol amine obtained by step (1) and end position dibromoalkane 4.0～6.0: 1.0 dispensing in molar ratio,
First the polar organic solvent of diallyl ethylol amine and its 1.5 times of volumes is added in reactor, then heat up 80～
100 DEG C, in N2The lower dropping end position dibromoalkane of protection, control time for adding then proceeded to reaction 18～28 little in 3 hours
When；Solvent is steamed, then decompression steams the complete diallyl ethylol amine of unreacted, reclaims into next round and reacts；Steaming excess
Deionized water dissolves, and adds the dichloromethane of overall solution volume 1/5～1/3, fully vibrates, stands 30min, point liquid, water phase
With activated carbon adsorption 1～4 time, filter, vacuum rotary steam obtains light yellow viscous liquid, mass percentage concentration is 60～70%, i.e., singly
Liquid solution.
(3) monomer solution obtained by step (2) is added in reactor, respectively by 0.8～the 1.2 ‰ of monomer mass, 1.5
～2.0 ‰ add EDTA and NaF dissolvings, then lead to N2Oxygen 30min is driven, 60～75 DEG C are warming up to, Deca monomer mass 2.0～
2.5% water-soluble azo class initiator, reacts 3～4 hours, obtains brittle solid material, deionized water wash to neutrality, Yu Zhen
Empty drying baker is dried to constant weight below 50 DEG C, obtains brittle solid material.
(4) solid matter obtained by step (3) is ground, crosses 100 mesh sieves, the iron salt for being added to 0.1～1mol/L is molten
In liquid, phosphate is subsequently adding so as to which concentration is 0.01～0.015mol/L；40～50 DEG C are warming up to, are dripped under agitation
Plus the aqueous slkali of 0.1mol/L, Discrete control solution ph：1. it is 2.5～3.0 first to control pH, is reacted 1～2 hour；2. by pH
Value was stepped up to 6.0 in 1 hour, added the Polyethylene Glycol of solid matter mass 0.5～0.8% to continue reaction 1 hour.
(5) mixture obtained by step (4) is filtered, first 2～4 times are washed with the dilute hydrochloric acid that pH is 5.5～6.0, Ran Houyong
Deionized water is washed till neutrality；It is placed in vacuum drying oven at 60 DEG C and is dried 4 hours, is subsequently placed in microwave synthesizer microwave radiation
1～2min, taking-up are placed in vacuum drying oven at 70 DEG C and continue to be dried 36～48 hours, obtain faint yellow or light brown loose porous
Material.
Further, the reactor in step (1) and step (2) carries condensing tube, constant pressure funnel and mechanical agitation；Step
Suddenly the reactor in (3) carries Dropping funnel and mechanical agitation.
Further, the end position dibromoalkane described in step (2) is Isosorbide-5-Nitrae-dibromobutane, 1.5- dibromo pentanes and 1,6- dibromo
Any one in hexane.
Further, during the polar organic solvent described in step (2) is isopropanol, DMF or Ketocyclopentane
Any one, preferred DMF.
Further, the water-soluble azo class initiator described in step (3) is two 2,2-Dimethylaziridine dihydrochloride of azo and azo
Any one in two isobutyl imidazoline hydrochlorides.
Further, the iron salt solutions described in step (4) are Fe (NO3)3Or Fe2(SO4)3Any one in solution.
Further, the phosphate described in step (4) is NaH2PO4、Na2HPO4、KH2PO4And K2HPO4In any one.
Further, the aqueous slkali described in step (4) is any one in ammonia or NaOH solution.
Further, the Polyethylene Glycol described in step (4) is any one in PEG-4000 or Polyethylene Glycol -600.
The present invention relates to load the mesh structural porous heavy-metal adsorption material and preparation method of nano-sized iron oxide.First with two allyls
Base amine and 2-chloroethyl alcohol are raw material, water is that solvent synthesizes diallyl ethylol amine, then organic molten in polarity with end position dibromoalkane
Agent carries out quaternized, double (bromination diallyl ethoxy alkylammonium) monomers of preparation；Then adopt free yl solution polymerization side
Formula synthetic mesh porous material, then be immersed in iron salt solutions, the hydroxyl of the hydrolysis fabricated in situ Fe by controlling Fe (III)-
Oxygen complex, makes the active group-OH on porous material hole wall that the hydroxyl-oxo conjunction of Fe (III) is participated in as structural constituent
In thing molecular network, then the hydroxyl-oxygen complex of Fe (III) is transformed into into ferrum oxide and nano-sized iron oxide is loaded to into porous material
On material.The present invention can press intramolecular cyclization-intermolecular chain respectively by two groups of quaternary diallyl ammonium groups in same monomer molecule
The reaction mechanism of growth generates macromolecule to build the framing structure of reticulated porous materials, and by way of fabricated in situ grows
Nano-sized iron oxide is loaded on the hole wall of porous material, makes the porous material of preparation both maintain preferable pore passage structure, and
Adsorbing material adsorption surface area is improved, while making the nano-sized iron oxide of load stably be attached on the hole wall of porous material, is improved
The adsorption of heavy metal ion, the stability of material and service life.
Compared to existing technology, the present invention has the following technical effect that：
(1) can respectively according to intramolecular cyclization-intermolecular by two groups of quaternary diallyl ammonium groups in same monomer molecule
The mechanism that chain increases generates macromolecule to build the pore passage structure of porous material, and gained duct is larger and more regular, and permeability is good,
Pass through and heavy metal ions in wastewater and hole wall and the contact of active group thereon in duct beneficial to waste water, improve process useless
The efficiency of water, overcomes most nano materials and only relies on high-ratio surface to adsorb so that the not high shortcoming for the treatment of effeciency, while gram
The shortcomings of having taken hydrophobic activated carbon duct and make it difficult for the aqueous solution of polarity to pass through.
(2) porous material is immersed in iron salt solutions, the Fe (III) of the hydrolysis fabricated in situ growth by controlling Fe (III)
Hydroxyl-oxygen complex, makes-the OH on porous material hole wall that the hydroxyl-oxo conjunction of Fe (III) is participated in as structural constituent
In thing molecular network, then the hydroxyl-oxygen complex of Fe (III) is transformed into into ferrum oxide and nano-sized iron oxide is loaded to into porous material
Mode on material, improves the stability of load nano-sized iron oxide, improves the service life of material；And nano oxidized iron particle is
With on hole wall ,-OH is distributed as basic point, therefore good dispersion, is not reunited, and is kept larger adsorption surface area, is improve
Absorbability.
(3) by load nano-sized iron oxide, improve adsorption surface area, can give full play to again ferrum oxide surface characteristic and
The characteristic of electric charge, so that the adsorption effect of heavy metal is significantly improved.
(4) the mesh structural porous heavy-metal adsorption material of load nano-sized iron oxide of the invention has good pore passage structure,
Higher specific surface area, excellent surface texture featur and stability, heavy metal ion have excellent adsorption effect, higher
Treatment effeciency, excellent zeolite regeneration performance, the heavy metal of absorption is easily recycled, and the service life cycle of material is long, reduces
The cost of water process.
(5) it is applied widely, the process of suitable various heavy metal wastewater therebies, particularly low concentration heavy metal water and waste water
Advanced treating, with wide application value.
Description of the drawings
Fig. 1 is the preparation technology FB(flow block) of the present invention.
Fig. 2 is schemed for the SEM of faint yellow brittle solid material and product obtained by the embodiment of the present invention 1.
A position that takes of energy spectrum analysis figures of the Fig. 3 for 1 products therefrom of the embodiment of the present invention, wherein energy spectrum analysiss is left figure
Middle part position on the upper side, i.e., shown in 1 in figure.
X-ray diffraction patterns of the Fig. 4 for 1 products therefrom of the embodiment of the present invention.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Preparation method of the embodiment 1～8 for the mesh structural porous heavy-metal adsorption material of load nano-sized iron oxide, embodiment 9
～10 is absorption property, zeolite regeneration and the recycling of the mesh structural porous heavy-metal adsorption material of load nano-sized iron oxide
Energy.
Referring to Fig. 1, it is the preparation technology FB(flow block) of the present invention, its specific embodiment is as follows：
Embodiment 1：
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 1.5: 1.0: 1.0 dispensing in molar ratio, first by 68.9mL diene
Propyl group amine and 68.9mL water are added to 500mL with condensing tube, constant pressure funnel and churned mechanically reactor, add
16.92g solid carbonic acid potassiums, are warming up to 60 DEG C, are slowly added dropwise 25mL 2-chloroethyl alcohols, drip off in 3h, then Deca 64.87g potassium carbonate
Saturated solution, adds in 2h, continues reaction 2h；It is transferred in separatory funnel, stands 30min, point liquid, oil phase Anhydrous potassium carbonate
It is dried, steams unreacted diallylamine 19.7mL and react into next round；Vacuum distillation collects 117 to -0.093MPa
～121 DEG C of fraction 42.3mL, i.e. intermediate product diallyl ethylol amine, yield 76.82%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and 1,4- dibromobutanes are matched somebody with somebody in molar ratio at 4.0: 1.0
Material, first by 42.3mL diallyls ethylol amine and 66.4mLN, dinethylformamide is added to 250mL with condensing tube, perseverance
Press Dropping funnel and mechanical agitation and lead to N2Exclude in the reactor of air, then heat up 90 DEG C, in N2The lower slow drop 1 of protection,
4- dibromobutane 8.7mL, add in 3h, then proceed to react 24h；Solvent is steamed, then decompression steams the complete centre of unreacted
Product 23.6mL, reclaims into next round and reacts；Steaming excess is dissolved in water, and adds 30mL dichloromethane, vibration to stand 30min,
Liquid, water is divided mutually with activated carbon adsorption 3 times, to filter, vacuum rotary steam obtains light yellow viscous liquid 54.49g, and mass percentage concentration is
60.12%, i.e. monomer solution, are 93.25% to the yield of Isosorbide-5-Nitrae-dibromobutane；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 26.2mg EDTA and 49.1mg NaF dissolving, then lead to N2Oxygen 30min is driven, 60 DEG C is warming up to, Deca monomer mass
Two 2,2-Dimethylaziridine dihydrochloride of 655.2mg azos, reacts 4.0h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 31.89g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 0.1mol/L's
Fe(NO3)3In solution, 120mg NaH are subsequently adding2PO4, 40 DEG C are warming up to, the ammonia of 0.1mol/L is slowly added dropwise under agitation
Solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, 100mg is added
PEG-4000 continues reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 3 times with the dilute hydrochloric acid that pH is 5.5, then deionized water
It is washed till neutrality；Being placed in vacuum drying oven and 4h being dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 2min, taking-up is put
Continue to be dried 36h at 70 DEG C in the vacuum drying oven, obtain faint yellow loose porous material 29.61g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 22.70%..
(U.S. PE is public in Spectrum One (B) FTIR infrared spectrometers for faint yellow brittle solid material obtained by step (3)
Department) on determine its infrared spectrum (KBr tablettings), absworption peak wave number (cm-1)：3493.24、2948.37、2847.53、1639.89、
1588.44、1431.47、1411.44、1349.17、1322.41、1139.02、1021.65、944.74、879.09、727.97、
619.29。
Faint yellow brittle solid material obtained by step (3)1H-NMR is composed in II NMR spectrometer with superconducting magnet of AVANCE
Determine in (German Bruker companies), absworption peak chemical shift (δ)：1.267 (main chain-CH 2-, 8H), 1.725～1.736 (N+- CH2- CH 2- CH 2- CH2- N+, 4H), 2.111～2.124 (pyrrole rings4H), 3.239～3.251 (N+-
CH 2- CH2- CH2- CH 2- N+, 4H), 3.332～3.361 (pyrrole ring N+- CH 2-, 4H), 3.427～3.436 (N+-
CH 2- CH2OH, 4H), 3.954～4.009 (N+- CH2- CH 2OH, 4H), 4.783 (OH, 2H).
By the pattern of faint yellow brittle solid material and product obtained by step (3) in JMS-6380LV type scanning electron microscopies
Mirror (Jeol Ltd.) is determined, and surface composition is surveyed using INCAX-SIGHT energy depressive spectroscopies (Oxford Instruments factory)
It is fixed, as a result see that Fig. 2, the SEM of wherein Fig. 2 (a) faint yellow brittle solid materials (unsupported ferrum oxide) obtained by step (3) shine
Piece, SEM photographs of the Fig. 2 (b) for product (load ferrum oxide).The netted of unsupported ferrum oxide be can be seen that from Fig. 2 (a) and (b)
Porous material hole wall smoother, and hole wall surface all has very thin powdered substance after loading ferrum oxide；From the power spectrum of Fig. 3
Analysis result can be seen that the atom hundred that the mass percent that the mass percent of O herein is 22.11%, Fe is 45.59%, O
It is 28.07% that fraction is the atomic percentage of 42.54%, Fe, and the atomic number ratio for calculating O and Fe is 1.5154: 1, closely
Fe2O3Middle O and Fe theory atomic numbeies compare 1.5: 1, show that the oxide for loading meets Fe2O3It is elementary composition.
The thing of product mutually adopts D/max-2550VB+18KW turns target x-ray diffractometer (Rigaku) and is measured (survey
Amount condition：40KV/250mA, 8 °/min of scanning speed, DS=1 ° of scanning slit, SS=1 °, RS=0.3mm, using graphite monochromatic
Device, RS=0.6mm), as a result see Fig. 4.As seen from Figure 4, the general performance of diffraction pattern is unformed feature, but in 2Theta
(°) is respectively 24.16,33.05,35.62,41.02,49.43,54.21,57.67,62.52,64.10 and 71.98 etc. to be occurred
Obvious spike, Jing is compareed with standard PDF card, with α-Fe2O3Characteristic diffraction peak is consistent, there is α-Fe in showing product2O3。
Comprehensive SEM, energy spectrum analysiss and X-ray diffraction analysis result, show nanometer α-Fe2O3Successfully it is supported on netted
The mesh structural porous heavy-metal adsorption material of load nano-sized iron oxide on porous material, is synthesized.
Embodiment 2：
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 2.0: 1.0: 1.02 dispensing in molar ratio, first by 91.8mL diene
Propyl group amine and 91.8mL water are added to 500mL with condensing tube, constant pressure funnel and churned mechanically reactor, add
17.25g solid carbonic acid potassiums, are warming up to 70 DEG C, are slowly added dropwise 25mL 2-chloroethyl alcohols, drip off in 3h, then Deca 66.17g potassium carbonate
Saturated solution, adds in 2h, continues reaction 1.5h；It is transferred in separatory funnel, stands 30min, point liquid, oil phase Carbon Dioxide
Potassium is dried, and steams unreacted diallylamine 43.1mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 45.5mL, i.e. intermediate product diallyl ethylol amine, yield 78.95%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and 1,4- dibromobutanes are matched somebody with somebody in molar ratio at 5.0: 1.0
45.5mL diallyls ethylol amine and 68.2mL isopropanols are first added to 250mL with condensing tube, constant pressure funnel by material
Lead to N with mechanical agitation and2Exclude in the reactor of air, then heat up 80 DEG C, in N2The lower slow drop 1,4- dibromobutanes of protection
Add in 7.1mL, 3h, then proceed to react 28h；Solvent is steamed, then decompression steams the complete intermediate product 28.3mL of unreacted,
Reclaim into next round and react；Steaming excess is dissolved in water, and adds 25mL dichloromethane, vibration to stand 30min, and point liquid, water are mutually used
Activated carbon adsorption 1 time, filters, and vacuum rotary steam obtains light yellow viscous liquid 41.69g, and mass percentage concentration is 65.27%, i.e., singly
Liquid solution, is 94.17% to the yield of Isosorbide-5-Nitrae-dibromobutane；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 27.2mg EDTA and 46.3mg NaF dissolving, then lead to N2Oxygen 30min is driven, 65 DEG C is warming up to, Deca monomer mass
Two isobutyl imidazoline hydrochloride of 598.6mg azos, reacts 3.5h, obtains brittle solid material, be washed with deionized to neutrality, in
Vacuum drying oven is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 26.47g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 0.5mol/L's
Fe(NO3)3In solution, 170.3mg Na are subsequently adding2HPO4, 45 DEG C are warming up to, are slowly added dropwise 0.1mol/L's under agitation
NaOH solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
120mg PEG-4000s continue reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 4 times with the dilute hydrochloric acid that pH is 5.8, then deionized water
It is washed till neutrality；Be placed in vacuum drying oven and 4h be dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 1.5min, take out
It is placed in vacuum drying oven and continues to be dried 42h at 70 DEG C, obtains faint yellow loose porous material 29.34g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 22.26%..
Embodiment 3
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 2.5: 1.0: 1.05 dispensing in molar ratio, first by 114.8mL bis-
Allyl amine and 114.8mL water are added to 500mL and carry in condensing tube, constant pressure funnel and churned mechanically reactor, then
17.76g solid carbonic acid potassiums are added, 75 DEG C is warming up to, is slowly added dropwise 25mL 2-chloroethyl alcohols, drips off in 3h, then Deca 68.12g carbon
Sour potassium saturated solution, adds in 2h, continues reaction 1h；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine 64.2mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 46.2mL, i.e. intermediate product diallyl ethylol amine, yield 80.12%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and 1,4- dibromobutanes are matched somebody with somebody in molar ratio at 6.0: 1.0
46.2mL diallyls ethylol amine and 69.3mL Ketocyclopentane are first added to 250mL with condensing tube, constant pressure funnel by material
Lead to N with mechanical agitation and2Exclude in the reactor of air, then heat up 100 DEG C, in N2The lower slow drop 1,4- dibromo fourths of protection
Alkane 6.0mL, adds in 3h, then proceedes to react 18h；Solvent is steamed, then decompression steams the complete intermediate product of unreacted
31.6mL, reclaims into next round and reacts；Steaming excess is dissolved in water, and adds 20mL dichloromethane, vibration to stand 30min, point
Liquid, water mutually with activated carbon adsorption 2 times, are filtered, and vacuum rotary steam obtains light yellow viscous liquid 32.94g, and mass percentage concentration is
70.00%, i.e. monomer solution, are 94.37% to the yield of Isosorbide-5-Nitrae-dibromobutane；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 28.4mg EDTA and 47.3mg NaF dissolving, then lead to N2Oxygen 30min is driven, 70 DEG C is warming up to, Deca monomer mass
Two isobutyl imidazoline hydrochloride of 591.5mg azos, reacts 3h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 22.67g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 1.0mol/L's
Fe(NO3)3In solution, 205.4mg KH are subsequently adding2PO4, 50 DEG C are warming up to, are slowly added dropwise 0.1mol/L's under agitation
NaOH solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
160mg PEG-4000s continue reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 3 times with the dilute hydrochloric acid that pH is 6.0, then deionized water
It is washed till neutrality；Be placed in vacuum drying oven and 4h be dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 2min, take out
It is placed in vacuum drying oven and continues to be dried 48h at 70 DEG C, obtains faint yellow loose porous material 28.84g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 21.43%..
Embodiment 4
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 3.0: 1.0: 1.02 dispensing in molar ratio, first by 137.7mL bis-
Allyl amine and 137.7mL water are added to 500mL and carry in condensing tube, constant pressure funnel and churned mechanically reactor, then
17.25g solid carbonic acid potassiums are added, 70 DEG C is warming up to, is slowly added dropwise 25mL 2-chloroethyl alcohols, drips off in 3h, then Deca 66.17g carbon
Sour potassium saturated solution, adds in 2h, continues reaction 2h；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine 88.7mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 46.3mL, i.e. intermediate product diallyl ethylol amine, yield 80.21%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and 1,4- dibromobutanes are matched somebody with somebody in molar ratio at 5.0: 1.0
46.3mL diallyls ethylol amine and 69.5mL Ketocyclopentane are first added to 250mL with condensing tube, constant pressure funnel by material
Lead to N with mechanical agitation and2Exclude in the reactor of air, then heat up 95 DEG C, in N2The lower slow drop 1,4- dibromobutanes of protection
Add in 7.2mL, 3h, then proceed to react 24h；Solvent is steamed, then decompression steams the complete intermediate product 28.9mL of unreacted,
Reclaim into next round and react；Steaming excess is dissolved in water, and adds 25mL dichloromethane, vibration to stand 30min, and point liquid, water are mutually used
Activated carbon adsorption 4 times, filters, and vacuum rotary steam obtains light yellow viscous liquid 42.50g, and mass percentage concentration is 64.85%, i.e., singly
Liquid solution, is 93.85% to the yield of Isosorbide-5-Nitrae-dibromobutane；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 24.8mg EDTA and 49.6mg NaF dissolving, then lead to N2Oxygen 30min is driven, 68 DEG C is warming up to, Deca monomer mass
Two isobutyl imidazoline hydrochloride of 633.9mg azos, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 26.11g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 0.5mol/L's
Fe2(SO4)3In solution, 226.4mg K are subsequently adding2HPO4, 50 DEG C are warming up to, are slowly added dropwise 0.1mol/L's under agitation
NaOH solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
140mg Polyethylene Glycol -600 continues reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 4 times with the dilute hydrochloric acid that pH is 6.0, then deionized water
It is washed till neutrality；Be placed in vacuum drying oven and 4h be dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 1.5min, take out
It is placed in vacuum drying oven and continues to be dried 44h at 70 DEG C, obtains faint yellow loose porous material 29.98g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 23.27%.
Embodiment 5
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 2.2: 1.0: 1.02 dispensing in molar ratio, first by 101.0mL bis-
Allyl amine and 101.0mL water are added to 500mL and carry in condensing tube, constant pressure funnel and churned mechanically reactor, then
17.25g solid carbonic acid potassiums are added, 65 DEG C is warming up to, is slowly added dropwise 25mL 2-chloroethyl alcohols, drips off in 3h, then Deca 66.17g carbon
Sour potassium saturated solution, adds in 2h, continues reaction 2h；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine 53.8mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 45.7mL, i.e. intermediate product diallyl ethylol amine, yield 79.29%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and pentamethylene bromide are matched somebody with somebody in molar ratio at 4.5: 1.0
46.3mL diallyls ethylol amine and 69.5mL Ketocyclopentane are first added to 250mL with condensing tube, constant pressure funnel by material
Lead to N with mechanical agitation and2Exclude in the reactor of air, then heat up 95 DEG C, in N2The lower slow drop pentamethylene bromide of protection
Add in 9.0mL, 3h, then proceed to react 26h；Solvent is steamed, then decompression steams the complete intermediate product 25.6mL of unreacted,
Reclaim into next round and react；Steaming excess is dissolved in water, and adds 20mL dichloromethane, vibration to stand 30min, and point liquid, water are mutually used
Activated carbon adsorption 3 times, filters, and vacuum rotary steam obtains light yellow viscous liquid 48.84g, and mass percentage concentration is 63.92%, i.e., singly
Liquid solution, is 94.16% to the yield of pentamethylene bromide；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 31.2mg EDTA and 50.0mg NaF dissolving, then lead to N2Oxygen 30min is driven, 70 DEG C is warming up to, Deca monomer mass
Two 2,2-Dimethylaziridine dihydrochloride of 749.3mg azos, reacts 3.5h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 29.86g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 0.3mol/L's
Fe2(SO4)3In solution, 156.0mg NaH are subsequently adding2PO4, 45 DEG C are warming up to, the ammonia of 0.1mol/L is slowly added dropwise under agitation
Aqueous solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
130mg Polyethylene Glycol -600 continues reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 2 times with the dilute hydrochloric acid that pH is 5.6, then deionized water
It is washed till neutrality；Being placed in vacuum drying oven and 4h being dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 1min, taking-up is put
Continue to be dried 48h at 70 DEG C in the vacuum drying oven, obtain faint yellow loose porous material 29.75g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 22.92%..
Faint yellow brittle solid material obtained by step (3) in Spectrum One (B) FTIR infrared spectrometers (U.S. PE
Company) on determine its infrared spectrum (KBr tablettings), absworption peak wave number (cm-1)：3449.77、2954.19、2832.74、
1639.52、1587.06、1443.22、1417.43、1345.35、1321.25、1176.48、1112.99、1047.53、
943.51、726.15、649.34、623.33。
Faint yellow brittle solid material obtained by step (3)1H-NMR is composed in II NMR spectrometer with superconducting magnet of AVANCE
Determine in (German Bruker companies), absworption peak chemical shift (δ)：1.271 (main chain-CH 2-, 8H), 1.282～1.301 (N+- CH2- CH2- CH 2- CH2- CH2- N+, 2H), 1.719～1.757 (N+- CH2- CH 2- CH2- CH 2- CH2- N+,
4H), 2.087～2.105 (pyrrole ring4H), 3.219～3.235 (N+- CH 2- CH2- CH2- CH2- CH 2- N+,
4H), 3.316～3.333 (pyrrole ring N+- CH 2-, 4H), 3.423～3.431 (N+- CH 2- CH2OH, 4H), 3.965～
4.021(N+- CH2- CH 2OH, 4H), 4.779 (- OH, 2H).
Embodiment 6
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 2.8: 1.0: 1.02 dispensing in molar ratio, first by 128.5mL bis-
Allyl amine and 128.5mL water are added to 500mL and carry in condensing tube, constant pressure funnel and churned mechanically reactor, then
17.25g solid carbonic acid potassiums are added, 70 DEG C is warming up to, is slowly added dropwise 25mL 2-chloroethyl alcohols, drips off in 3h, then Deca 66.17g carbon
Sour potassium saturated solution, adds in 2h, continues reaction 2h；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine 80.2mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 45.5mL, i.e. intermediate product diallyl ethylol amine, yield 78.95%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and pentamethylene bromide are matched somebody with somebody in molar ratio at 5.0: 1.0
Material, first by 45.5mL diallyls ethylol amine and 68.3mL DMFs be added to 250mL with condensing tube,
Constant pressure funnel and mechanical agitation have simultaneously led to N2Exclude in the reactor of air, then heat up 90 DEG C, in N2The lower slow drop of protection
Pentamethylene bromide 8.0mL, adds in 3h, then proceedes to react 28h；Steam solvent, then decompression steam unreacted it is complete in
Between product 28.4mL, reclaim into next round reaction；Steaming excess is dissolved in water, and adds 25mL dichloromethane, vibration to stand
30min, point liquid, water mutually with activated carbon adsorption 4 times, are filtered, and vacuum rotary steam obtains light yellow viscous liquid 42.01g, and quality percentage is dense
Spend for 66.43%, i.e. monomer solution, be 93.95% to the yield of pentamethylene bromide；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 30.7mg EDTA and 47.4mg NaF dissolving, then lead to N2Oxygen 30min is driven, 68 DEG C is warming up to, Deca monomer mass
Two 2,2-Dimethylaziridine dihydrochloride of 669.8mg azos, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 26.52g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 0.5mol/L's
Fe2(SO4)3In solution, 191.7mg KH are subsequently adding2PO4, 45 DEG C are warming up to, the ammonia of 0.1mol/L is slowly added dropwise under agitation
Aqueous solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
120mg Polyethylene Glycol -600 continues reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 2 times with the dilute hydrochloric acid that pH is 5.5, then deionized water
It is washed till neutrality；Be placed in vacuum drying oven and 4h be dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 1.5min, take out
It is placed in vacuum drying oven and continues to be dried 45h at 70 DEG C, obtains faint yellow loose porous material 28.85g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 21.45%.
Embodiment 7
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 2.6: 1.0: 1.03 dispensing in molar ratio, first by 119.4mL bis-
Allyl amine and 119.4mL water are added to 500mL and carry in condensing tube, constant pressure funnel and churned mechanically reactor, then
17.42g solid carbonic acid potassiums are added, 70 DEG C is warming up to, is slowly added dropwise 25mL 2-chloroethyl alcohols, drips off in 3h, then Deca 66.82g carbon
Sour potassium saturated solution, adds in 2h, continues reaction 2h；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine 71.9mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 46.1mL, i.e. intermediate product diallyl ethylol amine, yield 80.07%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and 1,6- dibromo-hexanes are matched somebody with somebody in molar ratio at 4.5: 1.0
Material, first by 46.1mL diallyls ethylol amine and 69.2mL DMFs be added to 250mL with condensing tube,
Constant pressure funnel and mechanical agitation have simultaneously led to N2Exclude in the reactor of air, then heat up 100 DEG C, in N2Protection is lower slow
Drop 1,6- dibromo-hexane 10.2mL, add in 3h, then proceed to react 18h；Solvent is steamed, then reducing pressure, it is complete to steam unreacted
Intermediate product 27.0mL, reclaims into next round and reacts；Steaming excess is dissolved in water, and adds 20mL dichloromethane, vibration to stand
30min, point liquid, water mutually with activated carbon adsorption 4 times, are filtered, and vacuum rotary steam obtains light yellow viscous liquid 47.00g, and quality percentage is dense
Spend for 68.25%, i.e. monomer solution, be 93.27% to the yield of 1,6- dibromo-hexanes；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 25.7mg EDTA and 60.9mg NaF dissolving, then lead to N2Oxygen 30min is driven, 65 DEG C is warming up to, Deca monomer mass
Two 2,2-Dimethylaziridine dihydrochloride of 641.6mg azos, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 30.85g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 0.2mol/L's
Fe2(SO4)3In solution, 261.3mg K are subsequently adding2HPO4, 50 DEG C are warming up to, are slowly added dropwise 0.1mol/L's under agitation
NaOH solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
135.0mg PEG-4000s continue reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 3 times with the dilute hydrochloric acid that pH is 5.5, then deionized water
It is washed till neutrality；Being placed in vacuum drying oven and 4h being dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 1min, taking-up is put
Continue to be dried 48h at 70 DEG C in the vacuum drying oven, obtain faint yellow loose porous material 29.46g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 22.45%..
Faint yellow brittle solid material obtained by step (3) in Spectrum One (B) FTIR infrared spectrometers (U.S. PE
Company) on determine its infrared spectrum (KBr tablettings), absworption peak wave number (cm-1)：3519.94、2936.29、2819.71、
1639.77、1583.53、1442.34、1417.01、1361.28、1165.43、1034.22、947.35、883.88、722.24、
631.26。
Faint yellow brittle solid material obtained by step (3)1H-NMR is composed in II superconduction NMR (Nuclear Magnetic Resonance) spectrum of AVANCE
Determine on instrument (German Bruker companies), absworption peak chemical shift (δ)：1.268 (main chain-CH 2-, 8H), 1.277～1.296
(N+- CH2- CH2- CH 2- CH 2- CH2- CH2- N+, 4H), 1.718～1.753 (N+- CH2- CH 2- CH2- CH2-
CH 2- CH2- N+, 4H), 2.095～2.111 (pyrrole rings4H), 3.224～3.239 (N+- CH 2- CH2- CH2-
CH2- CH2- CH 2- N+, 4H), 3.319～3.331 (pyrrole ring N+- CH 2-, 4H), 3.431～3.4391 (N+- CH 2-
CH2OH, 4H), 3.961～4.017 (N+- CH2- CH 2OH, 4H), 4.783 (- OH, 2H).
Embodiment 8
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 2.4: 1.0: 1.02 dispensing in molar ratio, first by 110.2mL bis-
Allyl amine and 110.2mL water are added to 500mL and carry in condensing tube, constant pressure funnel and churned mechanically reactor, then
17.25g solid carbonic acid potassiums are added, 70 DEG C is warming up to, is slowly added dropwise 25mL 2-chloroethyl alcohols, drips off in 3h, then Deca 66.17g carbon
Sour potassium saturated solution, adds in 2h, continues reaction 2h；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine 62.7mL and reacts into next round；Vacuum distillation is collected to -0.093MPa
117～121 DEG C of fraction 46.4mL, i.e. intermediate product diallyl ethylol amine, yield 80.54%；
(2) intermediate product diallyl ethylol amine obtained by step (1) and 1,6- dibromo-hexanes are matched somebody with somebody in molar ratio at 4.8: 1.0
46.4mL diallyls ethylol amine and 69.6mL isopropanolamines are first added to 250mL and are leaked with condensing tube, constant pressure addition by material
Bucket is with mechanical agitation and leads to N2Exclude in the reactor of air, then heat up 80 DEG C, in N2The lower slow drop 1,6- dibromos of protection oneself
Alkane 9.6mL, adds in 3h, then proceedes to react 28h；Solvent is steamed, then decompression steams the complete intermediate product of unreacted
28.2mL, reclaims into next round and reacts；Steaming excess is dissolved in water, and adds 30mL dichloromethane, vibration to stand 30min, point
Liquid, water mutually with activated carbon adsorption 1 time, are filtered, and vacuum rotary steam obtains light yellow viscous liquid 48.07g, and mass percentage concentration is
63.45%, i.e. monomer solution, are 94.06% to the yield of 1,6- dibromo-hexanes；
(3) monomer solution obtained by step (2) is added in 150mL band Dropping funnels and churned mechanically reactor, point
Not Jia Ru 30.5mg EDTA and 54.9mg NaF dissolving, then lead to N2Oxygen 30min is driven, 75 DEG C is warming up to, Deca monomer mass
Two 2,2-Dimethylaziridine dihydrochloride of 671.0mg azos, reacts 3h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying baker is dried to constant weight below 50 DEG C, obtains the faint yellow brittle solid materials of 29.72g.
(4) solid matter 20g obtained by taking step (3) is ground, and crosses 100 mesh sieves, is added to 100mL 1.0mol/L's
Fe(NO3)3In solution, 184.5mg Na are subsequently adding2HPO4, 48 DEG C are warming up to, the ammonia of 0.1mol/L is slowly added dropwise under agitation
Aqueous solution, is first controlled to 2.5～3.0 solution ph, reacts 2h；PH value is stepped up to into 6.0 in 1h again, is added
140mg Polyethylene Glycol -600 continues reaction 1h.
(5) mixture obtained by step (4) is filtered, first washs 3 times with the dilute hydrochloric acid that pH is 5.6, then deionized water
It is washed till neutrality；Being placed in vacuum drying oven and 4h being dried at 60 DEG C, be subsequently placed in microwave synthesizer microwave radiation 2min, taking-up is put
Continue to be dried 44h at 70 DEG C in the vacuum drying oven, obtain faint yellow loose porous material 29.73g.
Potassium dichromate method is adopted to determine the mass fraction of Fe in product for 22.90%.
Embodiment 9
1- is designated as with the sample of unsupported ferrum oxide obtained by embodiment 1,5. and 7 and load ferrum oxide as adsorbent, respectively
0#(unsupported), 1-1#(load), 5-0#(unsupported), 5-1#(load), 7-0#(unsupported) and 7-1#(load), prepares respectively
Simulation heavy metal water of the mass-volume concentration containing Cu (II), Pb (II), Cd (II), As (V) and Cr (VI) for 1000mg/L
Sample, with wood activated charcoal to compare adsorbing material.Adsorption test condition：(1) adsorption capacity is determined, and takes 100mL simulation weights respectively
Metal water sample is placed in 250mL conical flasks, is weighed the adsorbing material and activated carbon of the above-mentioned preparations of 0.1g, is placed on constant-temperature table,
4h is vibrated at 25 DEG C, filtered with 0.45 μm of micropore filter, survey on AA100 type Atomic Absorption Spectrometers (PE companies of the U.S.)
Fixed, the concentration of heavy metal ion after absorption calculates the adsorption capacity of adsorbing material；(2) adsorption time is determined, by above-mentioned test side
Method, is measured by sampling ion concentration by time interval of 10min, it is determined that reaching the time of saturation absorption；(3) heavy metal is desorbed back
Receive, adsorption saturation adsorbing material is filtered with 0.45 μm of micropore filter, be washed with deionized slough metal not to be adsorbed from
Son, is then added in the dilute hydrochloric acid that pH value is 5.0,1h is vibrated on shaking table, is filtered with 0.45 μm of micropore filter, then spend from
Sub- water washing, determines the amount of eluting heavy metal, calculates the response rate of heavy metal, as a result as shown in table 1.
The absorption property of 1 product heavy metal ion of the present invention of table
1 result of table shows that, compared with the porous adsorbing material without load ferrum oxide, product specific surface area of the present invention is obvious
Increase, the adsorption effect of Cu (II), Pb (II), Cd (II), As (V) and Cr (VI) plasma is significantly improved, adsorbance is long-range
In commercially available wood activated charcoal, the time for reaching saturated extent of adsorption has shortened, though elution property and heavy metal recovery rate have somewhat
Decline, but still keep the good response rate.
Embodiment 10
According to the test method of embodiment 9, it is considered in the loss of process of the test adsorbing material, 100 times of popularization, i.e.,
10g sampling tests are first taken, experimental scale is progressively reduced, the adsorbing material of zeolite regeneration is reused for into the suction of heavy metal ion
It is attached, regeneration to be investigated with the absorption to As (V) and situation is recycled, measure reaches the timing interval of saturated extent of adsorption and changes
For 5min, table 2 is to recycle the result of 10 times.
The recycling situation (by taking the absorption to As (V) as an example) of 2 product of the present invention of table
2 result of table shows that zeolite regeneration affects less to adsorption capacity, after load ferrum oxide, the increase of eluting difficulty, and absorption
Capacity declines relatively obvious；And the elution cycles of unsupported ferrum oxide are little using the time change for reaching saturation absorption, reclaim
Though rate has been reduced, reduce few.But the mesh structural porous heavy metal adsorption of load nano-sized iron oxide generally speaking, of the invention
Material has the advantages that heavy metal is easily recycled, regneration of adsorbent material and recycles that performance is excellent, service life is longer.
It is only presently preferred embodiments of the present invention above, above-mentioned design of the invention, those skilled in the art are gone back
The proportioning that can be given in the present invention and proportioning and process conditions etc. are combined, are converted in process condition range, class
As these conversion and modification belong to the present invention flesh and blood.
Claims (10)
1. it is a kind of load nano-sized iron oxide mesh structural porous heavy-metal adsorption material, which is faint yellow or the loose porous material of light brown
Material, the structural formula of main component is as shown in formula I：
In formula I, n is 4～6 integer.
2. described in claim 1 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, including with
Lower step：
(1) by diallylamine, 2-chloroethyl alcohol and potassium carbonate 1.5～3.0: 1: 1～1.05 dispensing in molar ratio, first by diallyl
Amine and its isopyknic water are added in reactor, are added the solid carbonic acid potassium of potassium carbonate total amount 1/3, are warming up to 60～75
DEG C, Deca 2-chloroethyl alcohol, time for adding control in 3 hours, the saturated solution that then Deca is made into by remaining potassium carbonate, during Deca
Between control in 2 hours, to continue reaction 1～2 hour；It is transferred in separatory funnel, stands 30min, point liquid, the anhydrous carbon of oil phase
Sour potassium is dried, and steams unreacted diallylamine and reacts into next round, and vacuum distillation obtains diallyl ethylol amine；
(2) diallyl ethylol amine obtained by step (1) and end position dibromoalkane 4.0～6.0: 1.0 dispensing in molar ratio, first will
The polar organic solvent of diallyl ethylol amine and its 1.5 times of volumes is added in reactor, is then heated up 80～100 DEG C,
In N2The lower dropping end position dibromoalkane of protection, time for adding control then proceeded to reaction 18～28 hours in 3 hours；Steam
Solvent, then decompression steam the complete diallyl ethylol amine of unreacted, reclaim into next round and react；Steaming excess deionization
Water dissolution, adds the dichloromethane of overall solution volume 1/5～1/3, fully vibrates, stand 30min, and point liquid, water mutually use activated carbon
Absorption 1～4 time, filters, and vacuum rotary steam obtains light yellow viscous liquid, and mass percentage concentration is 60～70%, i.e. monomer solution；
(3) monomer solution obtained by step (2) is added in reactor, respectively by 0.8～the 1.2 ‰ of monomer mass, 1.5～
2.0 ‰ adds EDTA and NaF dissolvings, then lead to N2Oxygen 30min is driven, 60～75 DEG C are warming up to, Deca monomer mass 2.0～
2.5% water-soluble azo class initiator, reacts 3～4 hours, obtains brittle solid material, deionized water wash to neutrality, Yu Zhen
Empty drying baker is dried to constant weight below 50 DEG C, obtains brittle solid material；
(4) solid matter obtained by step (3) is ground, crosses 100 mesh sieves, be added in the iron salt solutions of 0.1～1mol/L,
It is subsequently adding phosphate so as to which concentration is 0.01～0.015mol/L；40～50 DEG C are warming up to, under agitation Deca
The aqueous slkali of 0.1mol/L, Discrete control solution ph：1. it is 2.5～3.0 first to control pH, is reacted 1～2 hour；2. by pH value
6.0 are stepped up in 1 hour, add the Polyethylene Glycol of solid matter mass 0.5～0.8% to continue reaction 1 hour；
(5) mixture obtained by step (4) is filtered, is first washed 2～4 times with the dilute hydrochloric acid that pH is 5.5～6.0, then spend from
Son is washed to neutrality；Be placed in vacuum drying oven at 60 DEG C and be dried 4 hours, be subsequently placed in microwave synthesizer microwave radiation 1～
2min, taking-up are placed in vacuum drying oven at 70 DEG C and continue to be dried 36～48 hours, obtain the loose porous material of faint yellow or light brown
Material.
3. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is any one in 1,4- dibromobutanes, pentamethylene bromide and 1,6- dibromo-hexanes to state the end position dibromoalkane in step (2).
4. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is any one in isopropanol, N,N-dimethylformamide or Ketocyclopentane to state the polar organic solvent in step (2).
5. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is two isobutyl imidazoline hydrochloride of two 2,2-Dimethylaziridine dihydrochloride of azo and azo to state the water-soluble azo class initiator in step (3)
In any one.
6. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is Fe (NO to state the iron salt solutions in step (4)3)3Or Fe2(SO4)3Any one in solution.
7. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is NaH to state the phosphate in step (4)2PO4、Na2HPO4、KH2PO4And K2HPO4In any one.
8. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is any one in ammonia or NaOH solution to state the aqueous slkali in step (4).
9. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
It is any one in PEG-4000 or Polyethylene Glycol -600 to state the Polyethylene Glycol in step (4).
10. it is according to claim 2 load nano-sized iron oxide mesh structural porous heavy-metal adsorption material preparation method, institute
The reactor stated in step (1) and step (2) carries condensing tube, constant pressure funnel and mechanical agitation；In the step (3)
Reactor carries Dropping funnel and mechanical agitation.
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