CN104475065B - Efficient heavy-metal-ion absorbent material and preparation method thereof - Google Patents
Efficient heavy-metal-ion absorbent material and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses an efficient heavy-metal-ion absorbent material and a preparation method thereof. The preparation method comprises the following steps: by taking diallylamine, halogenated ethanol, halogenated acetone or halogenated ethyl acetate as raw materials, and taking water as a reaction medium, preparing substituted tertiary diallylamine under an alkaline condition, and introducing -OH, -CO, -COOR and the like having relatively affinity action on heavy metal ions in molecules; purifying for refinining, and then performing quaternary ammonium with end-site dibromoalkane in a polar organic solvent for synthesizing monomer molecules containing two groups of diallyl quaternary ammonium salt groups in the molecules; and by taking water-soluble azo initiator as an initiator, synthesizing the heavy-metal absorbent material in a manner of aqueous solution polymerization. The absorbent material disclosed by the invention is good in permeability, strong in adsorption capacity, excellent in heavy metal recovery, elution regeneration and cyclic use performance, suitable for adsorption treatments on a plurality of types of heavy-metal-ion wastewater, and wide in popularization and application values.
Description
Technical field
The invention belongs to heavy metal-polluted water treatment field, particularly to a kind of efficient heavy ion adsorbing material and its system
Preparation Method.
Background technology
Heavy metal such as lead, cadmium, mercury, chromium and metalloid arsenic etc. to people, animals and plants and microorganism, there is significant toxicity it is impossible to
It is degraded by microorganisms, and is easily enriched with vivo and causes notable poisonous effect, be the class pollution very harmful to the mankind
Thing.Heavy metal pollution has become global great environmental problem, Heavy Metal Pollution be always International Environmental Protection circle difficult point and
Study hotspot.China is in the rapid economic development phase, and the selecting and purchasing of heavy metal, smelting, processing and product manufacturing activity are increasingly
Increase, cause many heavy metals to enter in environment.In recent years, heavy metal pollution gradually highlights, and assumes situation occurred frequently.?
The process for treating heavy-metal waste water of research and development both at home and abroad, such as chemical precipitation method, ferrite process, absorption method, ion-exchange, film mistake
In the method such as filter, floatation and electrochemical method, absorption method due to be using porous solid material to heavy metal in waste water from
The suction-operated of son and heavy metal is removed, be therefore tailored to various different heavy metal wastewater therebies, particularly low concentration wastewater and
The advanced treating of waste water, and it is simple to operate, advantage of lower cost, and therefore absorption method is a kind of economical, effective and most pushes away
The process for treating heavy-metal waste water of wide using value.
Using Heavymetal Wastewater Treatment by Adsorption, it is critical only that the performance of adsorbent.The treatment effect of heavy metal wastewater thereby
Depend primarily on the specific surface area of adsorbent, the functional group in the architectural feature and surface in hole: (1) specific surface area determines material
Surface energy and the remaining field of force, determine Material Physics absorption property；(2) architectural feature (yardstick in hole and its distribution, the hole in hole
Shape and regularity etc.) determine absorption selectivity；(3) functional group on surface can be inhaled by chemistry and exchange mechanism
Attached, play a major role to the efficiency of absorption, capacity and selectively.Therefore, research and develop and adopt the suction for heavy metal containing wastewater treatment
Attached dose of need have larger specific surface area, good pore property and heavy metal ion and have the surface work compared with strong affinity
Can group.The adsorbent being presently used for heavy metal process by sources can be divided into natural adsorbent, synthetic adsorbent with chemical constitution
With several types such as biological adsorption agents.Natural adsorbent includes natural inorganic and Natural organic sorbents.Natural inorganic sorbents
Mainly there are bentonite, zeolite, kaolin, sepiolite, palygorskite and diatomite etc.；Natural organic sorbents mainly have wood-fibred,
Cornstalk, rice husk, wood chip, bark and shitosan etc..These sorbing materials have the advantages that inexpensive, nontoxic, be easy to get, but due to this
Defect on body structure, the adsorption capacity of heavy metal ion is less, selectively low, and regeneration is difficult, is also easy to produce and contains a huge sum of money in a large number
Belong to discarded object and cause secondary pollution.Synthetic adsorbent mainly has carbonaceous adsorbent, synthetic resin, poromerics etc..
Carbonaceous adsorbent mainly active charcoal, activated carbon fiber and CNT etc., is the adsorbent of a class hydrophobic type, relies primarily on it
High-ratio surface can carry out Adsorption of Heavy Metal Ions, and water quality treatment is extremely difficult to require.Synthetic resin is mainly polymerized by vinyl monomer
It is obtained, the sorbing material of different structure can be obtained by changing monomer composition and polymerization methodses, also can enter one by chemical reaction
One-step functional gives sorbing material special performance, and such as Nanjing University Liu Fuqiang teaches the n in aminomethyl polystyrene for the seminar
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
am,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), Peking University Zhai Maolin professor seminar connects metering system on amphipathic gel
Sour dimethylamine ethyl ester (cheng q, li c c, xu l, li j q, zhai m l.adsorption of cr () using
the amphiphilic gels based on dimethylaminoethyl methacrylate modified with
1-bromoalkanes.chem eng j, 2011,173 (1): 42-48.), also graft polypropylene acetoacetic ester on guar gum
(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.).These sorbing materials often only have relatively to certain or certain several ion
Good absorption property, and due to actual heavy metal wastewater thereby complicated component, these sorbing materials are poor to the adaptability of actual waste water,
Treatment effeciency not high it is difficult to reach intended effect.Biological adsorption material is using organism and its derivative, such as thalline, algae
Class and some cell extracts etc. carry out heavy-metal ion removal to the suction-operated of heavy metal ion in water.Although having process effect
Rate height, small investment, operating cost are low, non-secondary pollution the advantages of, but microorganism heavy metal has selectivity, to an actual huge sum of money
Belong to the bad adaptability of wastewater environment, be difficult to find a kind of microorganism pervasive to contents of many kinds of heavy metal ion, and strain improvement ratio
Relatively time-consuming, therefore, hinder its popularization and application.It can be seen that, the adsorbent of the studies above and application all haves the shortcomings that certain drawn game
Sex-limited, it is difficult to the reuse of heavy metal recovery and adsorbent especially with these sorbent treatment heavy metal wastewater therebies, to suction
Attached process lacks designability and controllability, is difficult to carry out adsorbing separation heavy metal according to the expectation of people.
Content of the invention
An object of the present invention is that the above-mentioned technology existing for the heavy-metal adsorption material researched and developed and apply is asked
Topic, provides a kind of new and effective mesh structural porous heavy-metal adsorption material.It is characterized in using two group of two allyl in monomer molecule
Based quaternary ammonium salt group can generate macromolecule according to intramolecular cyclization-molecular link chain growth pattern respectively and form mesh structural porous material
Material skeleton structure, what on mesh node and hole wall, distribution was abundant has the active group relatively pretended to contents of many kinds of heavy metal ion
Group, such as-oh ,-co- and-coor (na) etc., improve the absorption property of heavy metal ion；Meanwhile, there is regular hole knot
Structure and higher specific surface area, so as to have higher Penetration ration, improve the efficiency of wastewater treatment, and beneficial to heavy metal ion
Desorption with reclaim, and the regeneration of sorbing material and recycling.
The efficient heavy ion adsorbing material of the present invention, shown in its structural formula such as formula (), is faint yellow fragility porous material
Material.
In formula (), n is 4～6 integer.
Second object of the present invention is to provide the preparation method of above-mentioned efficient heavy ion adsorbing material, and it includes
Following steps:
(1) by diallylamine, halides and alkali 1.2～2.0: 1: 1～1.05 dispensing in molar ratio, first by diallyl
Amine and its isopyknic water are added in reactor, add the solid base of alkali total amount 1/3, are warming up to 50～70 DEG C, drip halogen
For thing, time for adding controlled in 3 hours, then dripped the saturated solution being made into by remaining alkali, and time for adding controlled at 2 hours
Interior, continue reaction 1～2 hour；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 2～3 times with organic solvent,
Combining extraction liquid, steams solvent；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine entrance next round anti-
Should, steaming excess is merged with the steaming excess of extraction, distills the tertiary diallylamine intermediate product that must replace；
(3) step (2) gained intermediate product and end position dibromoalkane 3.0～5.0: 1.0 dispensing in molar ratio, first will be with two
The isopyknic polar organic solvent of person and step (2) gained intermediate product are added in reactor, then heat up 80～100 DEG C,
In n2Protection lower dropping end position dibromoalkane, controls time for adding in 3 hours, then proceedes to react 18～48 hours；Steam
Solvent, then decompression steams the complete intermediate product of unreacted, reclaims and enters next round reaction；Steaming excess is dissolved in water, if being in
Cloudy state, then add the ethyl acetate of overall solution volume 1/5～1/3, vibration, stand 30min, point liquid, aqueous phase activated carbon
Absorption 1～4 time, filters, and vacuum rotary steam obtains light yellow viscous liquid, and mass percentage concentration is 65～70%, i.e. monomer solution；
(4) step (3) gained monomer solution is added in reactor, presses 0.5～1.0 ‰, the 1.0 of monomer mass respectively
～1.5 ‰ add edta and naf dissolving, then lead to n2Drive oxygen 30min, be warming up to 60～70 DEG C, dropping monomer mass 2.0～
2.5% water-soluble azo class initiator, reacts 3～4 hours, obtains brittle solid material, is washed with deionized to neutrality, in
Vacuum drying chamber is dried to constant weight below 50 DEG C, obtains faint yellow solid particle, i.e. product.
Further, the reactor in step (1) and step (3) carries condenser pipe, constant pressure funnel and mechanical agitation；Step
Suddenly the reactor in (4) carries dropping funel and mechanical agitation.
Further, the halides in step (1) are chlroacetone, bromacetone, ethyl chloroacetate, bromoacetate, chlorethanol
Or any one in bromoethanol, preferably ethyl chloroacetate, bromoacetate.
Further, the alkali described in step (1) is any one in sodium carbonate and potassium carbonate, preferably potassium carbonate.
Further, the organic solvent described in step (2) is ether or ethyl acetate.
Further, the end position dibromoalkane described in step (3) is Isosorbide-5-Nitrae-dibromobutane, 1.5- dibromo pentane and 1,6- dibromo
Any one in hexane.
Further, the polar organic solvent described in step (3) is n, any one in n- dimethylformamide or cyclopentanone,
Preferably n, n- dimethylformamide.
Further, the water-soluble azo class initiator described in step (4) is azo two NSC 18620 dihydrochloride and azo
Any one in two isobutyl imidazoline hydrochloride.
The present invention relates to a kind of efficient heavy sorbing material and preparation method thereof.First with diallylamine and halohydrin or
Halogen acetone or halo acid esters are raw material, the tertiary diallylamine that water replaces for solvent synthesis, then with end position dibromoalkane in pole
Property organic solvent carries out quaternized, is then refined, obtains the sticky monomer containing two groups of quaternary diallyl ammonium groups, adopts
Synthesize the mesh structural porous heavy-metal adsorption material of fragility with free yl solution polymerization mode.The present invention passes through in same monomer molecule
Two groups of quaternary diallyl ammonium groups can press the polymerization reaction mechanism netted knot of generation that intramolecular cyclization-intermolecular chain increases respectively
Structure material, builds the skeleton structure of reticulated porous materials, and has heavy metal ion when monomer synthesizes and relatively to pretend
Group accesses in monomer molecule, makes to be distributed abundant activated adoption group on porous material wall, improves heavy metal ion
Suction-operated, adsorption effect significantly improves.
Compared to existing technology, the present invention has the following technical effect that:
(1) can be respectively according to intramolecular cyclization-intermolecular by two groups of quaternary diallyl ammonium groups in same monomer molecule
The mechanism even increasing generates macromolecule, easily constructs the skeleton structure of more regular porous material, resulting materials mesh is relatively
Greatly, permeability is good, passes through in duct beneficial to waste water, improve process waste water efficiency, overcome most nano materials only according to
To adsorb by high-ratio surface, so that the not high shortcoming for the treatment of effeciency, to overcome hydrophobic activated carbon duct simultaneously and make it difficult for pole
The shortcomings of aqueous solution of property passes through.
(2) pass through to introduce-oh ,-co- ,-coor (na) isoreactivity group in monomer molecule, make the netted of synthesis
The group of abundant close heavy metal ion be distributed on porous material wall, be beneficial to when heavy metal ion is passed through be fixed in hole
On wall, and hole wall is netted, crisscross, substantially increases adsorption effect.
(3) reticulated porous materials of the present invention have excellent pore passage structure, are covered with abundant active group on hole wall, make
Material not only has excellent adsorption effect and higher treatment effeciency, and makes it have good heavy metal desorption and regeneration
Can, it is easy to the recycling of heavy metal recovery and sorbing material, improve service life.
(4) product of the present invention achieves the controllable standby of heavy metal porous adsorbing material, makes adsorption process have controllability,
Easily reach desired target.
(5) there is to contents of many kinds of heavy metal ion universality, produce in suitable industrial and agricultural production and people's life is various heavy
The process of metallic wastewater；And because it has good desorption desorption performance, heavy metal is easily recycled, and sorbing material is easy to again
Raw, service life cycle is long, is particularly suitable for the advanced treating of adsorbing and extracting, low concentration heavy metal water and the waste water of noble metal,
There is wide application value.
Brief description
Fig. 1 is the preparation technology FB(flow block) of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 products therefrom.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
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, ethyl chloroacetate and potassium carbonate 1.2: 1: 1 dispensing in molar ratio, first by 55.4ml diene
Propyl group amine and 55.4ml water are added to 500ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
17.02g solid carbonic acid potassium, is warming up to 50 DEG C, is slowly added dropwise 40ml ethyl chloroacetate, drips off in 3h, then drips 65.3g carbonic acid
Potassium saturated solution, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 5.1ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 8.5ml and enters
Enter next round reaction, steaming excess is merged with the steaming excess of extraction, vacuum distillation extremely -0.093mpa, the evaporating of 126～130 DEG C of collection
Divide 56.4ml, that is, the tertiary diallylamine intermediate product ethoxycarbonymetyl diallylamine replacing, yield 76.30%；
(3) step (2) gained intermediate product and Isosorbide-5-Nitrae-dibromobutane in molar ratio 3.0: 1.0, first by 55ml intermediate product
And 66.3mln, n- dimethylformamide is added to 250ml and carries condenser pipe, constant pressure funnel and mechanical agitation logical n2
Exclusion air reactor in, then heat up 80 DEG C, in n2Lower slowly dripping in Isosorbide-5-Nitrae-dibromobutane 11.3ml, 3h is protected to add
Complete, then proceed to react 48h；Steam solvent, then decompression steams the complete intermediate product 21.9ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 20ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 2
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 75.12g, mass percentage concentration is 65.01%, i.e. monomer solution, to 1,
The yield of 4- dibromobutane is 91.31%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
24.4mg edta and 48.8mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 60 DEG C, drip monomer mass
976.6mg azo two NSC 18620 dihydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying box is dried to constant weight below 50 DEG C, obtains 47.23g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure (kbr compressing tablet),
Absworption peak wave number (cm-1): 3421.52,2979.02,2929.08,2808.47,1743.25,1646.90,1596.20,
1437.95、1410.29、1355.74、1326.25、1240.10、1159.84、1109.91、1065.35、996.21、
920.15、720.11、661.26、629.76.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.056～1.069 (ch 3ch2-, 6h), 1.271 (main chain-ch 2-, 8h), 1.723～1.761 (n+- ch2- ch 2- ch 2- ch2- n+, 4h), 2.102～2.120 (pyrrole rings4h), 2.457～2.478
(ch3ch 2-, 4h), 3.234～3.249 (n+- ch 2- ch2- ch2- ch 2- n+, 4h), 3.329～3.357 (pyrrole ring n+- ch 2-, 4h), 4.127 (n+- ch 2- coo, 4h).
Embodiment 2:
(1) by diallylamine, ethyl chloroacetate and potassium carbonate 1.6: 1: 1.02 dispensing in molar ratio, first by 73.9ml bis-
Allyl amine and 73.9ml water are added to 500ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, then plus
Enter 17.37g solid carbonic acid potassium, be warming up to 60 DEG C, be slowly added dropwise 40ml ethyl chloroacetate, drip off in 3h, then drip 66.62g
Saturated solution of potassium carbonate, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted with ethyl acetate 2 times, merges
Extract, steams solvent, obtains 5.4ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine
25.2ml enters next round reaction, and steaming excess is merged with the steaming excess of extraction, vacuum distillation extremely -0.093mpa, and collection 126～
130 DEG C of cut 59.9ml, that is, the tertiary diallylamine intermediate product ethoxycarbonymetyl diallylamine replacing, yield
81.20%；
(3) step (2) gained intermediate product and Isosorbide-5-Nitrae-dibromobutane in molar ratio 4.0: 1.0, first will produce in the middle of 73.3ml
Thing and 84.6ml cyclopentanone are added to 250ml and carry condenser pipe, constant pressure funnel and mechanical agitation and led to n2Exclusion air
Reactor in, then heat up 90 DEG C, in n2Protection is lower slowly to drip Isosorbide-5-Nitrae-dibromobutane 11.3ml, adds, Ran Houji in 3h
Continuous reaction 36h；Steam solvent, then decompression steams the complete intermediate product 39.1ml of unreacted, reclaim and enter next round reaction；Steam
Excess is dissolved in water, and adds 30ml ethyl acetate, vibration, stands 30min, point liquid, and aqueous phase charcoal absorption 3 times is filtered, subtracted
Pressure revolving obtains light yellow viscous liquid 73.26g, and mass percentage concentration is 68.20%, i.e. monomer solution, to Isosorbide-5-Nitrae-dibromobutane
Yield be 93.43%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
37.5mg edta and 59.9mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 65 DEG C, drip monomer mass
1149.0mg azo two isobutyl imidazoline hydrochloride, reacts 3.5h, obtains brittle solid material, be washed with deionized to neutrality,
Dry to constant weight below 50 DEG C in vacuum drying chamber, obtain 47.99g faint yellow solid particle, that is, product is heavy metal ion adsorbed
Material.
Embodiment 3:
(1) by diallylamine, ethyl chloroacetate and potassium carbonate 2.0: 1: 1.05 dispensing in molar ratio, first by 92.4ml bis-
Allyl amine and 92.4ml water are added to 500ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, then plus
Enter 17.88g solid carbonic acid potassium, be warming up to 70 DEG C, be slowly added dropwise 40ml ethyl chloroacetate, drip off in 3h, then drip 68.57g
Saturated solution of potassium carbonate, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted with ethyl acetate 3 times, merges
Extract, steams solvent, obtains 6.7ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine
44.9ml enters next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, collection 126～
130 DEG C of cut 59.6ml, that is, the tertiary diallylamine intermediate product ethoxycarbonymetyl diallylamine replacing, yield
80.71%；
(3) step (2) gained intermediate product and Isosorbide-5-Nitrae-dibromobutane in molar ratio 5.0: 1.0, first will produce in the middle of 91.7ml
Thing and 103.0mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 500ml
n2Exclusion air reactor in, then heat up 100 DEG C, in n2Lower slowly dripping in Isosorbide-5-Nitrae-dibromobutane 11.3ml, 3h is protected to add
Complete, then proceed to react 24h；Steam solvent, then decompression steams the complete intermediate product 57.7ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 35ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 4
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 70.85g, mass percentage concentration is 70.00%, i.e. monomer solution, to 1,
The yield of 4- dibromobutane is 92.74%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
49.6mg edta and 74.4mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 70 DEG C, drip monomer mass
1240mg azo two isobutyl imidazoline hydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying box is dried to constant weight below 50 DEG C, obtains 47.83g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
Embodiment 4:
(1) Example 1 product 20g is finely ground with mortar, crosses 200 mesh sieves, is added to 250ml band mechanical agitation and returned cold
In the three-necked bottle of solidifying pipe, addition 100ml with ethanol and the mixed solvent for 1: 1 for the water volume ratio for the naoh concentration that solvent is prepared is
The mixed solution of 2mol/l, is warming up to 60 DEG C, is stirred at reflux 4h.
(2) mixture of step (1) is filtered, distillation is washed to middle meta-alkalescence, dry at 50 DEG C in vacuum drying chamber
Dry obtain pressed powder 18.92g to constant weight, that is, contain-coo-Heavy metal ion adsorbing material.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.263 (main chain-ch 2-, 8h), 1.719～1.757 (n+- ch2- ch 2- ch 2- ch2- n+,
4h), 2.110～2.127 (pyrrole ring4h), 3.237～3.251 (n+- ch 2- ch2- ch2- ch 2- n+, 4h),
3.331～3.359 (pyrrole ring n+- ch 2-, 4h), 4.133 (n+- ch 2- coo, 4h).Comparative example 1, belongs to
ch3ch2- on absworption peak disappear, hydrolysis of ester group.
Embodiment 5:
(1) by diallylamine, bromoacetate and sodium carbonate 1.5: 1: 1.05 dispensing in molar ratio, first by 50.0ml bis-
Allyl amine and 50ml water are added to 500ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
9.88g solid sodium carbonate, is warming up to 60 DEG C, is slowly added dropwise 30ml bromoacetate, drips off in 3h, then drips 113.5g carbonic acid
Sodium saturated solution, adds in 2h, continues reaction 1h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted with ethyl acetate 3 times, merges
Extract, steams solvent, obtains 6.3ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine
15.3ml enters next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, collection 126～
130 DEG C of cut 45.5ml, that is, the tertiary diallylamine intermediate product ethoxycarbonymetyl diallylamine replacing, yield
85.44%；
(3) step (2) gained intermediate product and 1, pentamethylene bromide in molar ratio 4.0: 1.0, first will produce in the middle of 57.7ml
Thing and 67.7mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 100 DEG C, in n2Lower slow dripping in 1, pentamethylene bromide 10ml, 3h is protected to add
Complete, then proceed to react 24h；Steam solvent, then decompression steams the complete intermediate product 30.9ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 20ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 1
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 59.73g, mass percentage concentration is 67.20%, i.e. monomer solution, to 1,
The yield of pentamethylene bromide is 93.07%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
32.1mg edta and 48.2mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 70 DEG C, drip monomer mass
802.8mg azo two NSC 18620 dihydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying box is dried to constant weight below 50 DEG C, obtains 38.92g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure, (kbr presses product
Piece), absworption peak wave number (cm-1): 3433.172,2973.51,2924.33,2815.33,1747.11,1643.27,1591.75,
1434.54、1415.21、1364.36、1325.13、1240.26、1130.84、1047.22、935.44、872.23、729.04、
635.13.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.054～1.068 (ch 3ch2-, 6h), 1.263 (main chain-ch 2-, 8h), 1.279～1.303 (n+- ch2- ch2- ch 2- ch2- ch2- n+, 2h), 1.727～1.765 (n+- ch2- ch 2- ch2- ch 2- ch2- n+,
4h), 2.094～2.112 (pyrrole ring4h), 2.453～2.475 (ch3ch 2-, 4h), 3.223～3.238 (n+-
ch 2- ch2- ch2- ch2- ch 2- n+, 4h), 3.321～3.349 (pyrrole ring n+- ch 2-, 4h), 4.135 (n+- ch 2-
Coo, 4h).
Embodiment 6:
(1) Example 5 product 15g is finely ground with mortar, crosses 200 mesh sieves, is added to 250ml band mechanical agitation and returned cold
In the three-necked bottle of solidifying pipe, addition 100ml with ethanol and the mixed solvent for 1: 1 for the water volume ratio for the naoh concentration that solvent is prepared is
The mixed solution of 3mol/l, is warming up to 60 DEG C, is stirred at reflux 3h.
(2) mixture of step (1) is filtered, distillation is washed to middle meta-alkalescence, dry at 50 DEG C in vacuum drying chamber
Dry obtain pressed powder 14.12g to constant weight, that is, contain-coo-Heavy metal ion adsorbing material.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.271 (main chain-ch 2-, 8h), 1.271～1.325 (n+- ch2- ch2- ch 2- ch2-
ch2- n+, 2h), 1.721～1.759 (n+- ch2- ch 2- ch2- ch 2- ch2- n+, 4h), 2.097～2.115 (pyrrole rings4h), 3.229～3.241 (n+- ch 2- ch2- ch2- ch2- ch 2- n+, 4h), 3.325～3.353 (pyrrole ring n+- ch 2-, 4h), 4.129 (n+- ch 2- coo, 4h).Comparative example 5, belong to ch3ch2- on absworption peak disappear, ester
Base hydrolyzes.
Embodiment 7:
(1) by diallylamine, ethyl chloroacetate and potassium carbonate 1.5: 1: 1.05 dispensing in molar ratio, first by 52.0ml bis-
Allyl amine and 52.0ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, then plus
Enter 13.41g solid carbonic acid potassium, be warming up to 70 DEG C, be slowly added dropwise 30ml ethyl chloroacetate, drip off in 3h, then drip 51.44g
Saturated solution of potassium carbonate, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted with ethyl acetate 2 times, merges
Extract, steams solvent, obtains 5.5ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine
16.2ml enters next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, collection 126～
130 DEG C of cut 45.2ml, that is, the tertiary diallylamine intermediate product ethoxycarbonymetyl diallylamine replacing, yield
81.62%；
(3) step (2) gained intermediate product and 1,6- dibromo-hexane in molar ratio 4.0: 1.0, first will produce in the middle of 51.4ml
Thing and 61.4mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 90 DEG C, in n2Protection is lower slowly to drip 1,6- dibromo-hexane 10ml, adds in 3h,
Then proceed to react 18h；Steam solvent, then decompression steams the complete intermediate product 27.7ml of unreacted, reclaims and enters next round
Reaction；Steaming excess is dissolved in water, and adds 25ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 1 time,
Filter, vacuum rotary steam obtains light yellow viscous liquid 54.30g, mass percentage concentration is 66.72%, i.e. monomer solution, to 1,6- bis-
The yield of bromohexane is 92.21%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
32.6mg edta and 47.1mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 70 DEG C, drip monomer mass
797.1mg azo two isobutyl imidazoline hydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying box is dried to constant weight below 50 DEG C, obtains 35.17g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure, (kbr presses product
Piece), absworption peak wave number (cm-1): 3442.21,2982.82,2921.42,2822.69,1744.52,1633.57,1598.22,
1439.45、1421.44、1358.91、1319.31、1240.39、1135.02、1039.56、936.55、887.54、733.29、
633.32.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.047～1.062 (ch 3ch2-, 6h), 1.259 (main chain-ch 2-, 8h), 1.282～1.307 (n+- ch2- ch2- ch 2- ch 2- ch2- ch2- n+, 4h), 1.733～1.771 (n+- ch2- ch 2- ch2- ch2- ch 2-
ch2- n+, 4h), 2.085～2.112 (pyrrole rings4h), 2.450～2.472 (ch3ch 2-, 4h), 3.223～
3.239(n+- ch 2- ch2- ch2- ch2- ch2- ch 2- n+, 4h), 3.315～3.343 (pyrrole ring n+- ch 2-, 4h),
4.126(n+- ch 2- coo, 4h).
Embodiment 8:
(1) Example 7 product 15g is finely ground with mortar, crosses 200 mesh sieves, is added to 250ml band mechanical agitation and returned cold
In the three-necked bottle of solidifying pipe, addition 100ml with ethanol and the mixed solvent for 1: 2 for the water volume ratio for the naoh concentration that solvent is prepared is
The mixed solution of 3mol/l, is warming up to 50 DEG C, is stirred at reflux 5h.
(2) mixture of step (1) is filtered, distillation is washed to middle meta-alkalescence, dry at 50 DEG C in vacuum drying chamber
Dry obtain pressed powder 14.22g to constant weight, that is, contain-coo-Heavy metal ion adsorbing material.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.263 (main chain-ch 2-, 8h), 1.279～1.304 (n+- ch2- ch2- ch 2- ch 2-
ch2- ch2- n+, 4h), 1.729～1.767 (n+- ch2- ch 2- ch2- ch2- ch 2- ch2- n+, 4h), 2.087～
2.113(4h), 3.217～3.234 (n+- ch 2- ch2- ch2- ch2- ch2- ch 2- n+, 4h), 3.315～
3.343 (pyrrole ring n+- ch 2-, 4h), 4.126 (n+- ch 2- coo, 4h).Comparative example 7, belong to ch3ch2- on
Absworption peak disappears, hydrolysis of ester group.
Embodiment 9:
(1) by diallylamine, chlorethanol and potassium carbonate 1.6: 1: 1.05 dispensing in molar ratio, first by 58.8ml bis- allyl
Base amine and 58.8ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
14.21g solid carbonic acid potassium, is warming up to 70 DEG C, is slowly added dropwise 20ml chlorethanol, drips off in 3h, then drips 54.51g potassium carbonate
Saturated solution, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 3.9ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 20.3ml and enters
Enter next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, the evaporating of 117～121 DEG C of collection
Divide 35.2ml, that is, the tertiary diallylamine intermediate product ethoxy diallylamine replacing, yield 76.34%；
(3) step (2) gained intermediate product and Isosorbide-5-Nitrae-dibromobutane in molar ratio 3.5: 1.0, first will produce in the middle of 35.2ml
Thing and 43.1mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 95 DEG C, in n2Lower slowly dripping in Isosorbide-5-Nitrae-dibromobutane 7.9ml, 3h is protected to add
Complete, then proceed to react 20h；Steam solvent, then decompression steams the complete intermediate product 26.1ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 20ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 2
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 57.88g, mass percentage concentration is 65.47%, i.e. monomer solution, to 1,
The yield of 4- dibromobutane is 93.17%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
28.4mg edta and 45.5mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 65 DEG C, drip monomer mass
758.0mg azo two isobutyl imidazoline hydrochloride, reacts 3.5h, obtains brittle solid material, is washed with deionized to neutrality, in
Vacuum drying chamber is dried to constant weight below 50 DEG C, obtains 36.92g faint yellow solid particle, i.e. the heavy metal ion adsorbed material of product
Material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure, (kbr presses product
Piece), 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.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (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 ring4h), 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).
Embodiment 10:
(1) by diallylamine, bromoethanol and potassium carbonate 1.5: 1: 1.02 dispensing in molar ratio, first by 63.5ml bis- allyl
Base amine and 63.5ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
15.91g solid carbonic acid potassium, is warming up to 65 DEG C, is slowly added dropwise 25ml bromoethanol, drips off in 3h, then drips 61.01g potassium carbonate
Saturated solution, adds in 2h, continues reaction 1h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 4.1ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 21.2ml and enters
Enter next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, the evaporating of 117～121 DEG C of collection
Divide 42.6ml, that is, the tertiary diallylamine intermediate product ethoxy diallylamine replacing, yield 80.15%；
(3) step (2) gained intermediate product and 1, pentamethylene bromide in molar ratio 3.6: 1.0, first will produce in the middle of 40.8ml
Thing and 50.8mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 95 DEG C, in n2Lower slow 1 of protection, adds in pentamethylene bromide 10ml, 3h,
Then proceed to react 20h；Steam solvent, then decompression steams the complete intermediate product 19.5ml of unreacted, reclaims and enters next round
Reaction；Steaming excess is dissolved in water, and adds 25ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 2 times,
Filter, vacuum rotary steam obtains light yellow viscous liquid 52.23g, mass percentage concentration is 66.71%, i.e. monomer solution, to 1,5- bis-
The yield of bromo pentane silane is 94.05%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
34.9mg edta and 45.3mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 70 DEG C, drip monomer mass
766.7mg azo two isobutyl imidazoline hydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying box is dried to constant weight below 50 DEG C, obtains 33.54g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure (kbr compressing tablet),
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.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (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 rings4h), 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 11:
(1) by diallylamine, chlorethanol and potassium carbonate 2.0: 1: 1.05 dispensing in molar ratio, first by 73.5ml bis- allyl
Base amine and 73.5ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
14.21g solid carbonic acid potassium, is warming up to 70 DEG C, is slowly added dropwise 20ml chlorethanol, drips off in 3h, then drips 54.51g potassium carbonate
Saturated solution, adds in 2h, continues reaction 1.5h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 4.2ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 36.2ml and enters
Enter next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, the evaporating of 117～121 DEG C of collection
Divide 36.1ml, that is, the tertiary diallylamine intermediate product ethoxy diallylamine replacing, yield 78.37%；
(3) step (2) gained intermediate product and 1,6- dibromo-hexane in molar ratio 3.5: 1.0, first will produce in the middle of 35.3ml
Thing and 45.3mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 100 DEG C, in n2Lower slowly dripping in 1,6- dibromo-hexane 10ml, 3h is protected to add
Complete, then proceed to react 24h；Steam solvent, then decompression steams the complete intermediate product 16.4ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 20ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 2
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 45.919g, mass percentage concentration is 69.25%, i.e. monomer solution, to 1,
The yield of 6- dibromo-hexane is 93.85%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
25.4mg edta and 38.2mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 65 DEG C, drip monomer mass
795.0mg azo two NSC 18620 dihydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying box is dried to constant weight below 50 DEG C, obtains 30.26g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure, (kbr presses product
Piece), 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.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (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 ring4h), 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 12
(1) by diallylamine, chlroacetone and potassium carbonate 2.0: 1: 1.02 dispensing in molar ratio, first by 61.8ml bis- allyl
Base amine and 61.8ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
11.61g solid carbonic acid potassium, is warming up to 70 DEG C, is slowly added dropwise 20ml chlroacetone, drips off in 3h, then drips 44.50g potassium carbonate
Saturated solution, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 3.5ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 28.5ml and enters
Enter next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, the evaporating of 107～111 DEG C of collection
Divide 32.6ml, that is, the tertiary diallylamine intermediate methyl carbonyl amide replacing, yield 77.18%；
(3) step (2) gained intermediate product and Isosorbide-5-Nitrae-dibromobutane in molar ratio 3.5: 1.0, first will produce in the middle of 32.6ml
Thing and 39.3mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 90 DEG C, in n2Lower slowly dripping in Isosorbide-5-Nitrae-dibromobutane 6.7ml, 3h is protected to add
Complete, then proceed to react 26h；Steam solvent, then decompression steams the complete intermediate product 15.6ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 25ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 2
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 40.02g, mass percentage concentration is 65.11%, i.e. monomer solution, to 1,
The yield of 4- dibromobutane is 91.42%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
13.0mg edta and 39.1mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 70 DEG C, drip monomer mass
521.2mg azo two isobutyl imidazoline hydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying box is dried to constant weight below 50 DEG C, obtains 24.87g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure, (kbr presses product
Piece), absworption peak wave number (cm-1): 3368.74,2956.73,2835.35,1713.97,1632.33,1584.09,1442.74,
1422.53、1375.71、1325.14、1157.04、1031.84、951.26、873.21、731.27、626.31.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.259 (main chain-ch 2-, 8h), 1.719～1.731 (n+- ch2- ch 2- ch 2- ch2- n+,
4h), 2.124 (- coch 3, 6h), 2.117～2.131 (pyrrole rings4h), 3.237～3.249 (n+- ch 2- ch2-
ch2- ch 2- n+, 4h), 3.331～3.355 (pyrrole ring n+- ch 2-, 4h), 4.421 (n+- ch 2- coch3, 4h).
Embodiment 13:
(1) by diallylamine, bromacetone and potassium carbonate 1.6: 1: 1 dispensing in molar ratio, first by 58.8ml diallyl
Amine and 58.8ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
13.54g solid carbonic acid potassium, is warming up to 60 DEG C, is slowly added dropwise 25ml bromacetone, drips off in 3h, then drips 51.89g potassium carbonate
Saturated solution, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 3.5ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 20.1ml and enters
Enter next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, the evaporating of 107～111 DEG C of collection
Divide 39.8ml, that is, the tertiary diallylamine intermediate methyl carbonyl amide replacing, yield 79.45%；
(3) step (2) gained intermediate product and 1, pentamethylene bromide in molar ratio 3.5: 1.0, first will produce in the middle of 39.8ml
Thing and 49.0mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 90 DEG C, in n2Lower slow dripping in 1, pentamethylene bromide 9.2ml, 3h is protected to add
Complete, then proceed to react 24h；Steam solvent, then decompression steams the complete intermediate product 18.8ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 20ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 3
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 48.07g, mass percentage concentration is 68.55%, i.e. monomer solution, to 1,
The yield of pentamethylene bromide is 92.11%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
29.7mg edta and 42.8mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 70 DEG C, drip monomer mass
757.9mg azo two isobutyl imidazoline hydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, Yu Zhen
Empty drying box is dried to constant weight below 50 DEG C, obtains 31.97g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure (kbr compressing tablet),
Absworption peak wave number (cm-1): 3431.24,2949.87,2837.48,1715.42,1635.37,1582.71,1447.35,
1414.27、1373.47、1326.52、1165.84、1122.33、1043.26、953.42、825.24、721.79、657.55、
624.66.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.255 (main chain-ch 2-, 8h), 1.267～1.286 (n+- ch2- ch2- ch 2- ch2-
ch2- n+, 2h), 1.727～1.752 (n+- ch2- ch 2- ch2- ch 2- ch2- n+, 4h), 2.903～2.121 (pyrrole rings4h), 2.135 (- coch 3, 6h), 3.211～3.227 (n+- ch 2- ch2- ch2- ch2- ch 2- n+, 4h),
3.313～3.330 (pyrrole ring n+- ch 2-, 4h), 4.411 (n+- ch 2- coch3, 4h).Embodiment 14:
(1) by diallylamine, bromacetone and potassium carbonate 2.0: 1: 1 dispensing in molar ratio, first by 73.5ml diallyl
Amine and 73.5ml water are added to 250ml and carry in condenser pipe, constant pressure funnel and churned mechanically reactor, add
13.54g solid carbonic acid potassium, is warming up to 60 DEG C, is slowly added dropwise 25ml bromacetone, drips off in 3h, then drips 51.89g potassium carbonate
Saturated solution, adds in 2h, continues reaction 2h；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 3 times with ether, merges extraction
Liquid, steams solvent, obtains 3.9ml steaming excess；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine 35.2ml and enters
Enter next round reaction；Steaming excess is merged with the steaming excess of extraction, vacuum distillation to -0.093mpa, the evaporating of 107～111 DEG C of collection
Divide 40.7ml, that is, the tertiary diallylamine intermediate methyl carbonyl amide replacing, yield 81.31%；
(3) step (2) gained intermediate product and 1,6- dibromo-hexane in molar ratio 3.7: 1.0, first will produce in the middle of 40.7ml
Thing and 50.7mln, it is with condenser pipe, constant pressure funnel and mechanical agitation and logical that n- dimethylformamide is added to 250ml
n2Exclusion air reactor in, then heat up 95 DEG C, in n2Lower slowly dripping in 1,6- dibromo-hexane 10.0ml, 3h is protected to add
Complete, then proceed to react 28h；Steam solvent, then decompression steams the complete intermediate product 20.0ml of unreacted, reclaims and enters next
Wheel reaction；Steaming excess is dissolved in water, and adds 30ml ethyl acetate, vibration, stands 30min, point liquid, aqueous phase charcoal absorption 2
Secondary, filter, vacuum rotary steam obtains light yellow viscous liquid 47.85g, mass percentage concentration is 69.82%, i.e. monomer solution, to 1,
The yield of 6- dibromo-hexane is 94.01%；
(4) step (3) gained monomer solution is added in 150ml band dropping funel and churned mechanically reactor, point
33.4mg edta and 50.1mg naf Jia Ru not dissolve, then lead to n2Drive oxygen 30min, be warming up to 65 DEG C, drip monomer mass
835.3mg azo two NSC 18620 dihydrochloride, reacts 4h, obtains brittle solid material, be washed with deionized to neutrality, in vacuum
Drying box is dried to constant weight below 50 DEG C, obtains 32.32g faint yellow solid particle, i.e. product heavy metal ion adsorbing material.
In spectrum one (b) ftir infrared spectrometer (pe company of the U.S.) its infrared spectrum of upper mensure, (kbr presses product
Piece), absworption peak wave number (cm-1): 3421.78,2945.54,2831.75,1716.24,1628.37,1579.44,1447.77,
1423.23、1358.23、1181.81、1036.19、960.39、889.05、733.33、628.27.
Product1H-nmr spectrum, in the upper mensure of avance NMR spectrometer with superconducting magnet (German bruker company), is inhaled
Receive peaking displacement study (δ): 1.281 (main chain-ch 2-, 8h), 1.279～1.23 (n+- ch2- ch2- ch 2- ch 2- ch2-
ch2- n+, 4h), 1.729～1.761 (n+- ch2- ch 2- ch2- ch2- ch 2- ch2- n+, 4h), 2.073～2.103
(pyrrole ring4h), 2.133 (- coch 3, 6h), 3.231～3.244 (n+- ch 2- ch2- ch2- ch2- ch2-
ch 2- n+, 4h), 3.323～3.335 (pyrrole ring n+- ch 2-, 4h), 4.395 (n+- ch 2- coch3, 4h).
With embodiment 1, embodiment 4～14 gained sample as adsorbent, it is designated as 1 respectively#、4#、5#、6#、7#、8#、9#、10#、
11#、12#、13#With 14#, prepare respectively and contain cu2+、ni2+、cd2+And pb2+Mass-volume concentration be 1000mg/l simulation a huge sum of money
Belong to water sample, with wood activated charcoal for compareing sorbing material.Adsorption test condition: (1) adsorption capacity measures, and takes 100ml mould respectively
Intend heavy metal water sample to be placed in 250ml conical flask, weigh sorbing material and the activated carbon of the above-mentioned preparation of 0.1g, be placed in constant-temperature table
On, vibrate 4h at 25 DEG C, filtered with 0.45 μm of millipore filter, on aa100 type Atomic Absorption Spectrometer (pe company of the U.S.)
Measure the concentration of heavy metal ion after adsorbing, calculate the adsorption capacity of sorbing material；(2) adsorption time measures, by above-mentioned test
Method, is measured by sampling ion concentration with 10min for time interval, determines the time reaching saturation absorption；(3) heavy metal is desorbed back
Receive, adsorption saturation sorbing material is filtered with 0.45 μm of millipore filter, be washed with deionized slough metal not to be adsorbed from
Son, is then added in the hydrochloric acid of 0.01mol/l, vibrates 1h, filtered with 0.45 μm of millipore filter, then use deionization on shaking table
Water washing, measures the amount of wash-out heavy metal, calculates the rate of recovery of heavy metal, and result is as shown in table 1.
The absorption property of table 1 product heavy metal ion of the present invention
It can be seen that, product of the present invention is to free cu2+、ni2+、cd2+、pb2+And zn2+Plasma all has preferable adsorption effect,
Its specific surface area is more much smaller than commercially available wood activated charcoal, but its adsorbance is much larger than activated carbon, reaches the time of saturated extent of adsorption
Also it is faster than activated carbon, and there is good elution property, therefore, heavy metal ion is easy to reclaim, and sorbing material is easy to regenerate
Recycle, will not produce containing the discarded object of heavy metal as activated carbon and cause secondary pollution；Adsorption capacity is to change
One-tenth-coo-Sorbing material maximum, the time reaching saturation absorption is the shortest, other containing-oh with-coch3Relatively, its
Reason is-coo-Easy and heavy metal ion forms stronger chemical bond.
According to above-mentioned test method it is considered to process of the test sorbing material loss, 100 times of popularization, first take
10g sampling test, progressively reduces experimental scale, the sorbing material of zeolite regeneration is reused for the absorption of heavy metal ion, with
To cu2+Absorption investigate regeneration and recycle situation, table 2 is to recycle the result of 10 times.
The recycling situation of table 2 product of the present invention is (with to cu2+Absorption as a example)
Table 2 result shows, zeolite regeneration affects very little to adsorption capacity, and 10 elution cycles use and reach saturation absorption
Time does not substantially change, though the rate of recovery has reduced, reduces few.Therefore, the heavy-metal adsorption material of the present invention has
The advantages of good heavy metal recovery, regneration of adsorbent material, recycling, service life are longer.
It is only presently preferred embodiments of the present invention above, according to the above-mentioned design of the present invention, those skilled in the art is also
In the proportioning that the present invention is given and process condition range, proportioning and process conditions etc. can be combined, convert, class
As these conversion and modification belong to the flesh and blood of the present invention.
Claims (9)
1. a kind of efficient heavy ion adsorbing material, it is faint yellow fragility porous material, the structural formula such as formula of main component
Shown in ():
In formula (), n is 4～6 integer.
2. the preparation method of the efficient heavy ion adsorbing material described in claim 1, comprises the following steps:
(1) by diallylamine, halides and alkali 1.2～2.0: 1: 1～1.05 dispensing in molar ratio, first by diallylamine and
Its isopyknic water is added in reactor, adds the solid base of alkali total amount 1/3, is warming up to 50～70 DEG C, drips halides,
Control time for adding in 3 hours, then drip the saturated solution being made into by remaining alkali, control time for adding in 2 hours, continue
Continuous reaction 1～2 hour；
(2) above-mentioned liquid phase is transferred in separatory funnel, stands 30min, point liquid, and aqueous phase is extracted 2～3 times with organic solvent, merges
Extract, steams solvent；Oil phase is dried with Anhydrous potassium carbonate, steams unreacted diallylamine and enters next round reaction, steams
Excess is merged with the steaming excess of extraction, distills the tertiary diallylamine intermediate product that must replace；
(3) step (2) gained intermediate product and end position dibromoalkane 3.0～5.0: 1.0 dispensing in molar ratio, first will be with both bodies
The isopyknic polar organic solvent of long-pending sum and step (2) gained intermediate product are added in reactor, then heat up 80～100
DEG C, in n2Protection lower dropping end position dibromoalkane, controls time for adding at 3 hours, then proceedes to react 18～48 hours；Steam
Solvent, then decompression steams the complete intermediate product of unreacted, reclaims and enters next round reaction；Steaming excess is dissolved in water, if being in
Cloudy state, then add the ethyl acetate of overall solution volume 1/5～1/3, vibration, stand 30min, point liquid, aqueous phase activated carbon
Absorption 1～4 time, filters, and vacuum rotary steam obtains light yellow viscous liquid, and mass percentage concentration is 65～70%, i.e. monomer solution；
(4) step (3) gained monomer solution is added in reactor, press respectively monomer mass 0.5～1.0 ‰, 1.0～
1.5 ‰ add edta and naf dissolving, then lead to n2Drive oxygen 30min, be warming up to 60～70 DEG C, dropping monomer mass 2.0～
2.5% water-soluble azo class initiator, reacts 3～4 hours, obtains brittle solid material, is washed with deionized to neutrality, in
Vacuum drying chamber is dried to constant weight below 50 DEG C, obtains faint yellow solid particle, i.e. product.
3. the preparation method of efficient heavy ion adsorbing material according to claim 2, the halogen in described step (1)
For thing be chlroacetone, any one in bromacetone, ethyl chloroacetate, bromoacetate, chlorethanol or bromoethanol.
4. the preparation method of a kind of efficient heavy ion adsorbing material according to claim 2, in described step (1)
Alkali be any one in sodium carbonate or potassium carbonate.
5. the preparation method of efficient heavy ion adsorbing material according to claim 2, having in described step (2)
Machine solvent is ether or ethyl acetate.
6. the preparation method of efficient heavy ion adsorbing material according to claim 2, the end in described step (3)
Position dibromoalkane is any one in 1,4- dibromobutane, 1.5- dibromo pentane and 1,6- dibromo-hexane.
7. the preparation method of efficient heavy ion adsorbing material according to claim 2, the pole in described step (3)
Property organic solvent be n, any one in n- dimethylformamide or cyclopentanone.
8. the preparation method of efficient heavy ion adsorbing material according to claim 2, the water in described step (4)
Soluble azo class initiator is any one in azo two NSC 18620 dihydrochloride and azo two isobutyl imidazoline hydrochloride.
9. the preparation method of efficient heavy ion adsorbing material according to claim 2, described step (1) and step
(3) reactor in carries condenser pipe, constant pressure funnel and mechanical agitation；Reactor in step (4) carries dropping funel
And mechanical agitation.
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