CN106395965A - Method used for high efficiency adsorbing of heavy metals with functionalized magnetic material rich in thio amino groups - Google Patents
Method used for high efficiency adsorbing of heavy metals with functionalized magnetic material rich in thio amino groups Download PDFInfo
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- CN106395965A CN106395965A CN201610882135.4A CN201610882135A CN106395965A CN 106395965 A CN106395965 A CN 106395965A CN 201610882135 A CN201610882135 A CN 201610882135A CN 106395965 A CN106395965 A CN 106395965A
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention provides a method used for high efficiency adsorbing of heavy metals with a functionalized magnetic material rich in thio amino groups, relates to preparation of a thio amino functional group modified hyperbranched polymer magnetic material, belongs to the field of functional material and heavy metal adsorption, and more specifically relates to removing of Pb2+, Cu2+, Cd2+, and Hg2+ in aqueous solutions with a hyperbranched polymer functionalized magnetic compound material with terminal amino groups modified with sulfur-containing chelation groups via static adsorption. The terminal amino group hyperbranched polymer contains a high molecular weight polymer with a network ball similar three-dimensional structure which is capable of increasing the density of surface functional groups. Compared with linear polymers, the polymer with the hyperbranched structures possesses following advantages: molecular chain entanglement is not easily caused, solubility is high, viscosity is low, the molecular structure is spherical, the interior of the polymer is provided with a large amounts of cavities, and the molecular surfaces possess a large number of reaction active sites, so that it is benefit for introduction of certain chelation groups, and the polymer is capable of increasing adsorbing efficiency in application in adsorption field. The polymer is capable of removing heavy metal ions such as Pb2+, Cu2+, Cd2+, and Hg2+ in aqueous solutions completely; the adsorbing materials are widely available; cost is low; operation is simple; removing effect is achieved quickly; and efficiency, selectivity, and adsorption capacity are high.
Description
Technical field
The present invention relates to functional material and heavy metal adsorption processing technology field, specifically, it is related to one kind rich in thio
The method of functional amido magnetic material efficient absorption heavy metal.
Background technology
With the fast development of global industry, heavy metal has become as a serious environmental problem to the pollution of water,
Because they have detrimental effect to the ecosystem and human health.Mining, Treatment of Metal Surface, application, typography, agriculture
The industries such as medicine, chemical fertilizer are discharged into the activities to nature or people for the heavy metal such as copper in environment, chromium, cadmium, lead, zinc, mercury, nickel or arsenic
Lead to grave consequences.These heavy metals enter water body environment, and hypertoxic, the carcinogenic and mutagenicity of just having at low concentrations is asked
Topic, can lead to a large amount of fishes and shrimps in water body dead；And due to there is disguise, accumulation property and being difficult to biodegradable, by food
The transmission of chain, the heavy metal of low concentration finally can be with the concentration enrichment of ill-effect in humans and animals body, may induction people
Body gene mutation, in addition dead, great damage is caused to people and animals.Therefore, for optimizing the living environment of the mankind, reduce health danger
Evil, reduce waste water in harmful heavy metal pollutant so as to reach discharging standards, have become as when this year society extremely urgent
Top priority.
Absorption method is due to low cost, good adsorption performance it is considered to be the most effectively removing heavy metal pollution of water body
One of method of thing.Sorbent material is the key of absorption method, and magnetic nanometer adsorbent material has that specific surface area is big, superparamagnetic
Property, separate easily from solution, hypotoxicity and surface are easy to the features such as modify, and have very wide application in water treatment field
Prospect.Lot of documents is had to report the preparation method of functional amido magnetic Nano material at present, respectively " one-step method " and " two
Two methods of footwork ".Comparatively speaking, " one-step method " preparation method is simple, the magnetic-particle stability prepared and dispersiveness
Preferably, it is favourable for sorbing material.The amidine functional group on the mesoporous magnetic-particle surface that " but one-step method " is prepared
Density is little, and that is, adsorption site is less, adsorption capacity and the rate of adsorption relatively low be its subject matter.
Over-expense polymer is that one kind is rich in various functional end-groups, has the big of the spherical 3-D solid structure of similar network
Molecularly Imprinted Polymer, it can increase the density of surface functional group.For comparing linear polymer, the polymer of highly branched structure its
Not easy entanglement between strand, solubility is high, and viscosity is low, and molecular structure is spherical in shape, and there are substantial amounts of cavity, the reaction of molecule in inside
Avtive spot is more, is conducive to the introducing of specific chelating functional group, is applied to adsorbing domain, is greatly improved adsorption capacity
And efficiency.Compared with dendrimers molecule, dissaving polymer synthesis technique is simple, and only one-step method just can synthesize, and no
Need to purify it is easy to industrialized production.The a large amount of active function groups in dissaving polymer surface can be prepared not by modifying and decorating
The polymer of congeniality and function, it is also possible to modify in other base materials such as material surface such as mesoporous silicon oxide, magnetic material, carries
High surface functional group density, improves the limitation that base material itself is brought.
Sulfur-bearing heavy metal chelating group can form stable complex compound with a lot of heavy metals, and the present invention is by hyperbranched polymerization
Thing, the advantage of magnetic material are combined with heavy metal chelating group, prepare a kind of rich based on modifying containing thio amidine functional group
Magnetic material, realizes quick, the efficient absorption of Heavy Metals in Waters ion are removed, has broad application prospects.
Content of the invention
The present invention is directed to the deficiency of current magnetic adsorptive material, proposes a kind of dissaving polymer using compound with regular structure and carries
The method of high magnetic material surface sulfur-bearing chelation group density, prepares one kind and is rich in thioamido functional magnetic material, and
Realize the efficient absorption of heavy metal.
The technical solution used in the present invention is as follows：
Initially with vacuum condensation methods preparation end amino superbranching polymer, " one kettle way " is then adopted to prepare surface band amine
The mesoporous magnetic material of base, under crosslinking agent effect, end amino superbranching polymer is crosslinked with mesoporous magnetic material, finally exist
Under alkalescence condition, react with sulfur-bearing chelation group, preparation is rich in thioamido functional magnetic material, and provides this functionalization
Magnetic material under certain pH conditions, the method for heavy metal ion in efficient absorption water.
A kind of preparation rich in thioamido functional magnetic material and the method for efficient absorption heavy metal, walk including following
Suddenly：
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：Monomer A is dissolved the monomer B then dripping equimolar number in methyl alcohol,
After reaction 8～14h under room temperature, vacuum distillation goes out the methyl alcohol in system, then 40～80 DEG C of continuation reaction 0.5～3h under vacuum,
It is warming up to 100～150 DEG C of reaction 6～10h.Methyl alcohol dissolving is added, product precipitates through ether, filtering and washing, very after the completion of reaction
Sky is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous FeCl3With sodium acetate according to 1: 4～8 mol ratio
It is dissolved in ethylene glycol, stirs ultrasonic 0.5～1h, then under 30～50 DEG C of counterflow conditions, rub according to sodium acetate etc.
Your amount adds amino-contained reagent, reacts 1～3h.To react under the conditions of 180～220 DEG C in autoclave of gained mixture
6～12h, then deionized water and absolute ethanol washing products therefrom, 24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) products therefrom is dispersed in phosphoric acid
In cushioning liquid (the amino superbranching polymer concentration containing end is 5～20g/L), and adjust pH value, after ultrasonic 10～20min, plus
Enter 4～8mL crosslinking agent, then heat to mechanic whirl-nett reaction 6～12h under logical condition of nitrogen gas between 50～85 DEG C, products therefrom
Deionized water and absolute ethanol washing 5 times, are dried 12h in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 200～
After ultrasonic 15～30min in the sodium hydroxide solution of 500mL 0.1～0.5mol/L, add 40～80mL isopropanol, Ran Houzai
Add 4～10mL sulfur-bearing heavy metal chelating group, then mechanical agitation 4～8h at ambient temperature, products obtained therefrom deionization
Water and isopropanol wash 5 times, and Magneto separate is dried 10h in 40 DEG C of vacuum drying chambers；
B. in water, the efficient absorption of heavy metal ion is applied
Take a certain amount of be placed in the aqueous solution containing heavy metal ion rich in thioamido functional magnetic material, adjust
PH value, stirring is lower to adsorb.
It is an advantage of the current invention that：
1. with the mesoporous magnetic material of functional amido as base material, using its high-specific surface area, good stability, dispersiveness
And separation function, in grafting, there is the hyperbranched poly that a large amount of active function groups are contained on spheroidal three-dimensional structure cavity and surface
Compound, can increase substantially the functional group densities of adsorbent surface, realize the rapidly and efficiently absorption of heavy metal in water.
2. prepare functional amido magnetic material initially with " one kettle way ", have that method is simple, structural property is stable, point
The advantages of scattered property is preferable.Amido over-expense polymer will be held to be grafted on functional amido magnetic material using crosslinking agent, there is conjunction
The advantage such as one-tenth process is simple, cycle is short, efficiency are higher, with low cost, it is easy to accomplish industrialized production.
3. the present invention introduces thioamido functional group on the functionalized magnetic material surface of end amido over-expense, not only carries
The high density of sorbing material surface functional group, and also improve adsorptive selectivity and the efficiency of heavy metal.Gained is combined
Material is easily isolated recovery, safety non-toxic, environmental protection, and application prospect is extensive.
Brief description
Fig. 1 is infrared spectrogram (a) the functional amido magnetic mesoporous material of case study on implementation 1 of the present invention, and (b) end amido surpasses
Branched polymer functional magnetic material, (c) is rich in the infrared comparison diagram of thioamido functional magnetic material；
Fig. 2 is (a) transmission rich in thioamido functional magnetic material and (b) scanning electricity of case study on implementation 1 of the present invention
Mirror figure；
Fig. 3 is for various materials in case study on implementation 1 of the present invention to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Static Adsorption
Block diagram, (a) functional amido magnetic mesoporous material, (b) holds the functionalized magnetic material of amino superbranching, and (c) is rich in
Thioamido functional magnetic material.
Specific embodiment
Below in conjunction with the accompanying drawings and be embodied as case technical solution of the present invention is further elaborated.
Embodiment 1
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：20.63g diethylenetriamine is dissolved in 25mL methyl alcohol, then drips
The methyl acrylate of 17.22g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then the lower 60 DEG C of continuation of vacuum
Reaction 1h, oil bath is warming up to 100-150 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, and suction filtration is washed
Wash, vacuum drying obtains faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL monoethanolamine reaction 2.5h.Gained is mixed
Reaction 10h under the conditions of 200 DEG C in autoclave of compound, then deionized water and absolute ethanol washing products therefrom,
24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent glutaraldehyde, then heat to mechanic whirl-nett reaction under logical condition of nitrogen gas between 60 DEG C
10h, products therefrom deionized water and absolute ethanol washing 5 times, are dried 12h in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mLCS2, Ran Hou
Mechanical agitation 8h under room temperature condition, products obtained therefrom deionized water and isopropanol wash 5 times, Magneto separate, are vacuum dried at 40 DEG C
Case is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 100%.
Embodiment 2
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：12.02g ethylenediamine is dissolved in 25mL methyl alcohol, then drips
The methyl acrylate of 17.22g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then the lower 60 DEG C of continuation of vacuum
Reaction 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, filtering and washing, very
Sky is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL reacting ethylenediamine 2.5h.Gained is mixed
Reaction 10h under the conditions of 200 DEG C in autoclave of compound, then deionized water and absolute ethanol washing products therefrom,
24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent epoxychloropropane, then heat to mechanical agitation under logical condition of nitrogen gas between 60 DEG C anti-
Answer 10h, products therefrom deionized water and absolute ethanol washing 5 times, 12h is dried in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL isothiocyanic acid
Ester, then mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, and Magneto separate, at 40 DEG C
Vacuum drying chamber is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 99%.
Embodiment 3
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：29.29g TEPA is dissolved in 25mL methyl alcohol, then drips
The ethyl acrylate of 22.83g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then the lower 60 DEG C of continuation of vacuum
Reaction 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, filtering and washing, very
Sky is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL diethylenetriamine reaction 2.5h.By institute
10h is reacted, then deionized water and absolute ethanol washing gained produce under the conditions of obtaining 200 DEG C in autoclave of mixture
Thing, is dried 24h in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent epoxychloropropane, then heat to mechanical agitation under logical condition of nitrogen gas between 60 DEG C anti-
Answer 10h, products therefrom deionized water and absolute ethanol washing 5 times, 12h is dried in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL benzoyl sulphur
Urea, then mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, and Magneto separate, at 40 DEG C
Vacuum drying chamber is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 98%.
Embodiment 4
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：29.29g TEPA is dissolved in 25mL methyl alcohol, then drips
The succinic anhydride of 20.01g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, and then lower 60 DEG C of vacuum continues instead
Answer 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, filtering and washing, vacuum
It is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL triethylene tetramine reaction 2.5h.By institute
10h is reacted, then deionized water and absolute ethanol washing gained produce under the conditions of obtaining 200 DEG C in autoclave of mixture
Thing, is dried 24h in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent epoxychloropropane, then heat to mechanical agitation under logical condition of nitrogen gas between 60 DEG C anti-
Answer 10h, products therefrom deionized water and absolute ethanol washing 5 times, 12h is dried in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL sulfydryl benzo thiophene
Azoles, then mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, and Magneto separate, at 40 DEG C
Vacuum drying chamber is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 98%.
Embodiment 5
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：20.63g diethylenetriamine is dissolved in 25mL methyl alcohol, then drips
The methyl acrylate of 17.22g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then the lower 60 DEG C of continuation of vacuum
Reaction 1h, oil bath is warming up to 100-150 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, and suction filtration is washed
Wash, vacuum drying obtains faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL monoethanolamine reaction 2.5h.Gained is mixed
Reaction 10h under the conditions of 200 DEG C in autoclave of compound, then deionized water and absolute ethanol washing products therefrom,
24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent epoxychloropropane, then heat to mechanical agitation under logical condition of nitrogen gas between 60 DEG C anti-
Answer 10h, products therefrom deionized water and absolute ethanol washing 5 times, 12h is dried in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL isothiocyanic acid
Ester, then mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, and Magneto separate, at 40 DEG C
Vacuum drying chamber is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 99%.
Embodiment 6
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：12.02g ethylenediamine is dissolved in 25mL methyl alcohol, then drips
The methyl acrylate of 17.22g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then the lower 60 DEG C of continuation of vacuum
Reaction 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, filtering and washing, very
Sky is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL diethylenetriamine reaction 2.5h.By institute
10h is reacted, then deionized water and absolute ethanol washing gained produce under the conditions of obtaining 200 DEG C in autoclave of mixture
Thing, is dried 24h in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent epoxychloropropane, then heat to mechanical agitation under logical condition of nitrogen gas between 60 DEG C anti-
Answer 10h, products therefrom deionized water and absolute ethanol washing 5 times, 12h is dried in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL thiocarbamide, then
Mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, Magneto separate, do in 40 DEG C of vacuum
Dry case is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 98%.
Embodiment 7
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：41.67g five vinyl hexamine is dissolved in 25mL methyl alcohol, then drips
Plus the phthalic anhydride of 29.63g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then lower 60 DEG C of vacuum
Continue reaction 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, and suction filtration is washed
Wash, vacuum drying obtains faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL reacting ethylenediamine 2.5h.Gained is mixed
Reaction 10h under the conditions of 200 DEG C in autoclave of compound, then deionized water and absolute ethanol washing products therefrom,
24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent epoxychloropropane, then heat to mechanical agitation under logical condition of nitrogen gas between 60 DEG C anti-
Answer 10h, products therefrom deionized water and absolute ethanol washing 5 times, 12h is dried in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL carbon disulfide,
Then mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, Magneto separate, true at 40 DEG C
Empty drying box is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 98%.
Embodiment 8
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：12.02g ethylenediamine is dissolved in 25mL methyl alcohol, then drips
The ring butyric anhydride of 17.22g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, and then lower 60 DEG C of vacuum continues instead
Answer 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, filtering and washing, vacuum
It is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g FeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL o-phenylenediamine reaction 2.5h.By gained
Reaction 10h under the conditions of 200 DEG C in autoclave of mixture, then deionized water and absolute ethanol washing products therefrom,
24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent hexahydrophthalic anhydride, then heat to machinery under logical condition of nitrogen gas between 60 DEG C
Stirring reaction 10h, products therefrom deionized water and absolute ethanol washing 5 times, are dried 12h in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL sulfydryl benzo thiophene
Azoles, then mechanical agitation 8h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, and Magneto separate, at 40 DEG C
Vacuum drying chamber is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 98%.
Embodiment 9
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：12.02g ethylenediamine is dissolved in 25mL methyl alcohol, then drips
The methyl acrylate of 17.22g, after reaction 10h under room temperature, vacuum distillation goes out the methyl alcohol in system, then the lower 60 DEG C of continuation of vacuum
Reaction 1h, oil bath is warming up to 125 DEG C of reaction 8.5h.Add methyl alcohol dissolving, reactant mixture precipitates through ether, filtering and washing, very
Sky is dried to obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous for 2.0g EeCl3It is dissolved in 60mL with 4.0g sodium acetate
Ethylene glycol in, stir ultrasonic 1h, under 40 DEG C of counterflow conditions, then add 20mL o-phenylenediamine reaction 2.5h.By gained
Reaction 10h under the conditions of 200 DEG C in autoclave of mixture, then deionized water and absolute ethanol washing products therefrom,
24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) the material 300mg for preparing divides
It is dispersed in 100mL phosphate buffer solution (the amino superbranching polymer concentration containing end is 20g/L), and adjust pH value for 7.0 about,
After ultrasonic 15min, add 6mL crosslinking agent glutaraldehyde, then heat to mechanic whirl-nett reaction under logical condition of nitrogen gas between 60 DEG C
10h, products therefrom deionized water and absolute ethanol washing 5 times, are dried 12h in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 380mL
After ultrasonic 15-30min in the sodium hydroxide solution of 0.1mol/L, add 60mL isopropanol, then add 6mL benzoyl sulphur
Urea, then mechanical agitation 10h at ambient temperature, products obtained therefrom deionized water and isopropanol wash 5 times, and Magneto separate, 40
DEG C vacuum drying chamber is dried 10h.
B. in water, the efficient absorption of heavy metal ion is applied
Weigh 50mg rich in thioamido functional magnetic material, be placed in containing Pb2+、Cu2+、Cd2+、Hg2+50mL water
In, initial concentration is 12mg/L, and pH value is adjusted to 6.0,25 DEG C of constant temperature, and water-bath vibration 1h takes out, rich in thioamido functionalization
Magnetic material is to Pb in the aqueous solution2+、Cu2+、Cd2+、Hg2+Clearance all close to 95%.
Claims (7)
1. a kind of method rich in thioamido functional magnetic material efficient absorption heavy metal, including rich in thioamido function
In the preparation of change magnetic material and water, the efficient absorption application of heavy metal ion, specific as follows：
A. it is rich in the preparation of thioamido functional magnetic material
1) end amido overspends the preparation of polymer：Monomer A is dissolved the monomer B then dripping equimolar number in methyl alcohol, room temperature
After lower reaction 8～14h, vacuum distillation goes out the methyl alcohol in system, and then 40～80 DEG C of continuation reaction 0.5～3h under vacuum, heat up
To 100～150 DEG C of reaction 6～10h.Methyl alcohol dissolving is added, product precipitates through ether, filtering and washing, and vacuum is done after the completion of reaction
Dry obtain faint yellow viscous solid；
2) preparation of the mesoporous magnetic material of functional amido：By anhydrous FeCl3It is dissolved according to 1: 4～8 mol ratio with sodium acetate
In ethylene glycol, the ultrasonic 0.5～1h of stirring about, then under 30～50 DEG C of counterflow conditions, according to amount equimolar with sodium acetate
Add amino-contained reagent, react 1～3h.By reaction under the conditions of 180～220 DEG C in autoclave of gained mixture 6～
12h, then deionized water and absolute ethanol washing products therefrom, 24h is dried in 60 DEG C of vacuum drying chambers；
3) end amido overspends the preparation of functionalized mesoporous magnetic material：By step 2) products therefrom is dispersed in phosphoric acid buffer
Solution (containing end amino superbranching polymer concentration be 5～20g/L) in, and adjust pH value, after ultrasonic 10～20min, add 4～
8mL crosslinking agent, then heats between 50～85 DEG C mechanic whirl-nett reaction 6～12h under logical condition of nitrogen gas, products therefrom spend from
Sub- water and absolute ethanol washing 5 times, are dried 12h in 60 DEG C of vacuum drying chambers；
4) it is rich in the preparation of thioamido functional magnetic material：Taking step 3) products therefrom 200mg is dispersed in 200～
After ultrasonic 15～30min in the sodium hydroxide solution of 500mL0.1～0.5mol/L, add 40～80mL isopropanol, then add again
Enter 4～10mL sulfur-bearing heavy metal chelating group, then mechanical agitation 4～8h at ambient temperature, products obtained therefrom deionized water
Wash 5 times with isopropanol, Magneto separate, 10h is dried in 40 DEG C of vacuum drying chambers；
B. in water, the efficient absorption of heavy metal ion is applied
Take a certain amount of be placed in the aqueous solution containing heavy metal ion rich in thioamido functional magnetic material, adjust pH value,
Stirring is lower to adsorb.
2. according to claim 1 it is characterised in that：Monomer A described in step a is ethylenediamine, diethylenetriamine, triethylene four
One of amine, TEPA, five vinyl hexamines, described monomer B is succinic anhydride, phthalic anhydride, ring butyric acid
One of acid anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid.
One of acrylic acid, methacrylic acid.
3. according to claim 1 it is characterised in that：Amino-contained reagent described in step a is ethylenediamine, ethamine alcohol, divinyl
One of triamine, triethylene tetramine, TEPA, o-phenylenediamine, 1,6- hexamethylene diamine or several.
4. according to claim 1 it is characterised in that：Crosslinking agent described in step a is glutaraldehyde, epoxychloropropane, hexahydro are adjacent
One of phthalate anhydride etc. or multiple.
5. according to claim 1 it is characterised in that：Phosphate buffer solution described in step a is sodium dihydrogen phosphate and phosphoric acid hydrogen
Disodium or potassium dihydrogen phosphate and dipotassium hydrogen phosphate are blended with water, and pH is 6～8.
6. according to claim 1 it is characterised in that：Sulfur-bearing heavy metal chelating functional group described in step a is carbon disulfide, sulphur
One of urea, isothiocyanates, benzoylthioureas, mercaptobenzothiazoler or several.
7. according to claim 1 it is characterised in that：In step b, solution ph is allocated with NaOH and HCl, and pH is 2～8.
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