CN107961767A - A kind of adsorbent of aminodithioformic acid functionalization and preparation method and application - Google Patents
A kind of adsorbent of aminodithioformic acid functionalization and preparation method and application Download PDFInfo
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- CN107961767A CN107961767A CN201711097643.2A CN201711097643A CN107961767A CN 107961767 A CN107961767 A CN 107961767A CN 201711097643 A CN201711097643 A CN 201711097643A CN 107961767 A CN107961767 A CN 107961767A
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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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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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
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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
- C02F1/285—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to a kind of adsorbent of aminodithioformic acid functionalization and preparation method and application, adsorbent includes tree-shaped two parent of porous carrier and load on porous support, tree-shaped two parent is made of hydrophilic core and the oleophylic shell being covalently coated on outside hydrophilic core, hydrophilic core is the poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, and oleophylic shell is lipophilic cpd：During preparation, using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as dispersed phase, concentrated emulsions are formed, by polymerization, washing；In application, it is in 4 11 water, for adsorbing heavy metal ion by adsorbent input pH value.Compared with prior art, the present invention can not only efficiently catch metal ion and other pollutants, dispose most of heavy metal ion in water, while can easily and effectively be separated from the water again, excellent combination property.
Description
Technical field
The invention belongs to sorbing material technical field, is related to a kind of adsorbent and its system of aminodithioformic acid functionalization
Preparation Method and application.
Background technology
The removing of water pollutant is the common challenge that the whole mankind faces.On the one hand, industrialization, urbanization and population increase
Clean water is set to become shorter；On the other hand, global water supply and unbalanced, it is also possible to the persisting regressions of polar glacier
And reduce year by year.Conventional method for treating water, such as chemical oxidization method, Ozone, chlorine method, ammonia process, although pollutant can be reduced
Content, but it is not ideal enough for the treatment effect of the traces pollutant of low concentration；Absorption method is welcome processing method
One of, but most adsorbents are nearly unavailable to low-dose polluted thing.In addition, with industry particularly mining industry, smelting industry, chemical industry
With the development of pharmaceuticals industry etc., the species of water pollutant drastically increases, and huge challenge and height are brought to detection and processing
High cost.Heavy metal is the pollutant being widely present, with mining and smelting activity progress, many heavy metals by lithosphere into
Enter the ecosphere, start to influence ecological environment.Heavy metal species is more, existence form is various, toxicity is larger, can not degrade, and can hold
Toxic action is produced long, and the mankind are caused a significant threat.
Fat polyamine is because its metal coordination can adsorb various heavy, such as in porous two with specific pore size
The concentration of copper ion in water can be down to about 0.2ppm (referring to document by the polyamines that the regular hole surface of silica is introduced into：Dai S.,
Burleigh M.C.,Shin Y.S.,Morrow C.C.,Barnes C.E.Xue Z.L.A Novel Synthesis of
Selective Functionalized Ordered Mesoporous Sorbents[J]
.Angew.Chem.Int.Ed.1999,38(9),1235-1239).But fat polyamine is usually weaker with the effect of metal kind,
Metal residual concentration is high；Mercaptan and the effect of heavy metal kind are usually stronger, but mercaptan easily aoxidizes, and stability is poor.In addition,
The common carrier of these adsorbents is porous silica and magnetic iron oxide particle, but these carriers is undersized, it is difficult to
Separated from water simple and effective.Water process includes at least two essential aspects：Efficiently catch pollutant and conveniently have
The separation of effect ground.The essence efficiently caught is supramolecular chemistry problem, it is necessary to the supramolecular design based on molecular level.Many nanometers
Material is only capable of meeting at first point, and most macroscopical sorbing materials then mainly meet second point, can have this 2 points material concurrently at the same time
Material almost without.
Poly- High Internal Phase Emulsion is the classical way for preparing macropore macroscopic material, can easily provide a kind of porous framework.But
Expressed by Small molecular surfactant on its usual surface, it is impossible to undertake reliable adsorption function.Application publication number is
The Chinese invention patent of CN104437430A discloses a kind of high surface area porous sorbing material, and the patented technology is by tree-shaped amphiphilic
Body expresses the anionic property organic pollution and oleophylic aromatic hydrocarbons in porous material surface, energy high-efficient cleaning water removal securely, makes this
Pollutant residual concentration is reduced to ppb grades.But such adsorbent is not suitable for mainly for anionic property organic matter and aromatic hydrocarbons
The absorption of heavy metal.
Therefore, it is necessary to develop it is a kind of for heavy metal, surface fine functionalization, it is porous, there is macro-size
Adsorbent.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of dithiocarbamates first
Adsorbent of acid functionalization and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of adsorbent of aminodithioformic acid functionalization, the adsorbent include porous carrier and are supported on porous load
Tree-shaped two parent on body, tree-shaped two parent are made of hydrophilic core and the oleophylic shell being coated on outside hydrophilic core, the parent
Water core is the poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, and the oleophylic shell is oleophylic chemical combination
Thing.
As preferable technical solution, the poly- Ethylenimine is branched poly- Ethylenimine.
As preferable technical solution, in tree-shaped two parent, aminodithioformic acid root anionic functional group's
Mass percentage is 5-28%, and the mass percentage of lipophilic cpd is 68-91%.
Further, the porous carrier is formed by oiliness organic polymer.
Further, the oiliness organic matter includes one or both of alkene or alkadienes.
As preferable technical solution, in the oiliness organic matter, the molar ratio of alkene and alkadienes is 2:8-9:1.
Further, the oiliness organic matter includes crystallinity glycol, amorphism glycol and polyisocyanate, described
Crystallinity glycol be esterdiol in poly- alkylene, the amorphism glycol is ployalkylene glycol or dimethyl silicone polymer two
Alcohol.
Further, the lipophilic cpd is more than 12 lipophilic molecules for carbon number.
Further, the lipophilic cpd is hexadecane, polystyrene, polysiloxanes, poly- (styrene-co- methyl
Acrylate) or polypropylene glycol.
Further, it is connected directly between the hydrophilic core and oleophylic shell or is connected by 2- hydroxyl trimethylene bases.
When being connected directly between hydrophilic core and oleophylic shell, the structural formula of tree-shaped two parent is as shown in Equation 1：
When being connected between hydrophilic core and oleophylic shell by 2- hydroxyl trimethylene bases, the structural formula such as institute of formula 2 of tree-shaped two parent
Show：
In tree-shaped two parent, hydrophilic core for poly- Ethylenimine parent (PEI, molecular weight more than 800, for brevity, formula 1
Only depict a small amount of PEI repetitive units with formula 2) on carry multiple aminodithioformic acid root (DTC) anionic functional groups, oleophylic
Shell is lipophilic cpd (P), after hydrophilic core is connected with oleophylic shell by one of two ways, forms PEI-DTC@P.
A kind of preparation method of the adsorbent of aminodithioformic acid functionalization, this method are using tree-shaped two parent as stabilization
Agent, using oil phase as continuous phase, using water as dispersed phase, forms concentrated emulsions, by polymerization, washing, that is, obtains the absorption
Agent.
When oiliness organic matter is olefin/diene hydrocarbon, the oil phase containing stabilizer includes following components and parts by weight content：
Shown alkene is included in styrene, acrylate, methacrylate, acrylamide or Methacrylamide
It is one or more of.
Wherein, the ester group of acrylate and methacrylate is the fat-based containing 2 or more than 2 carbon atoms；Propylene
Two fatty substituents are carried on the N of acid amides and Methacrylamide, and the sum of carbon atom is more than 4 in fatty substituents.
The alkadienes includes polyethyleneglycol diacrylate (the ethylene glycol degree of polymerization is 1-12), polyethylene glycol dimethyl
Acrylate (the ethylene glycol degree of polymerization is 1-12), alkylene bisacrylamide (alkylene base carbon number 1-6), isoprene or two
One or more in vinyl benzene.
The solvent includes one or more of in alkylbenzene or halogenated hydrocarbons (boiling point is higher than 65 DEG C).
The radical initiator is azodiisobutyronitrile or benzoyl peroxide.
When oiliness organic matter is crystallinity glycol, amorphism glycol and polyisocyanate, the oil phase containing stabilizer
Including following components and parts by weight content：
The polyisocyanate is preferably polyethylene diphenylmethane diisocyanate (pMDI).
The organic solvent is that can dissolve organic phase component and the compound dissolved each other of discord water, including benzene, alkylbenzene or
It is one or more of in halogenated hydrocarbons.
As preferable technical solution, the volume ratio of the continuous phase and dispersed phase is 1:3.5-6.
Further, it is described to be polymerized to radical polymerization or polycondensation.It is dense when oiliness organic matter is olefin/diene hydrocarbon
The curing of lotion carry out by the way of radical polymerization for (70-80 DEG C) using heating；When oiliness organic matter for crystallinity glycol,
When amorphism glycol and polyisocyanate, the curing of concentrated emulsions using room temperature by the way of polycondensation hatch.
A kind of application of the adsorbent of aminodithioformic acid functionalization, the water for being 4-11 by adsorbent input pH value
In, for adsorbing heavy metal ion.Block porous adsorbent is direct plungeed into water, is (to be preferably in the range of 4-11 in pH value
It is neutral) all adsorbable metal ion, directly block adsorbent is pulled out after having adsorbed；Also sun can be adsorbed in alkaline conditions
Ionic dye and cationic surfactant.
In the present invention, multiple aminodithioformic acid roots are first introduced on poly- Ethylenimine, afterwards partially alkylated formation
Tree-shaped two parent；Using tree-shaped two parent as stabilizer, using olefin/diene hydrocarbon (or polyester-diol/polyisocyanate) as
Polymerizable oiliness organic matter, and add solvent etc. and form continuous phase, using water droplet as dispersed phase, oil is formed after being sufficiently stirred
Water-in type concentrated emulsions, after the aggregated curing of the concentrated emulsions (heating polymerization or room temperature polycondensation), are washed and dried with ethanol, had
There is the through hole bulk adsorbent of macro-size.Obtained adsorbent is expressed by the PEI-DTC on the hole surface of porous carrier.The suction
Attached dose carries out functional modification by aminodithioformic acid root anionic functional group to the hole surface of porous carrier, can be to a variety of
Metal is caught, various heavy metal ion such as copper ion, cadmium ion, lead ion in effective Adsorption water, and two thio ammonia
The stability of base formate is good, has a variety of combinations with metal kind.In addition, under the conditions of meta-alkalescence, which can be high
Effect removes the dye of positive ion and cationic surfactant.
Adsorbent produced by the present invention is in use, directly put into porous adsorbent quiet in the water containing heavy metal cation
Put or gentle agitation, pH value range 4-9 are preferably neutral.Directly porous adsorbent is pulled out after the completion of absorption, extruding removes
Moisture therein.Being calculated by adsorbance, the ratio of general metal pollutant/adsorbent in not less than 0.03mmol/g is launched,
General 4-8 days for the treatment of time of water.The adsorbent in alkaline conditions also has the dye of positive ion and cationic surfactant
Extraordinary adsorption effect.
For remaining heavy metal ion in the water sample after detection process, with inductance Induced Plasma spectral detection.Processing
Residual heavy metal ion in water afterwards, its residual concentration is generally at 0.05-15ppm grades.This adsorbent to copper ion, cadmium ion and
Lead ion is especially effective, and residual concentration is following at ppm grades, and especially the residual concentration of copper ion is in 0.05ppm or so.
Such adsorbent can be pulled out directly after having adsorbed from water, will not feed water and bring secondary pollution.After absorption
(pH in porous adsorbent input acid water<3) metal ion, adsorbed can partly discharge, to recover the absorption of adsorbent
Performance.In order to be thus capable of sufficiently recovering its absorption property, adsorbent, its adsorption capacity can be handled with carbon disulfide again in alkaline conditions
Can largely it recover.
Compared with prior art, the invention has the characteristics that：
1) the poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups is gathered by High Internal Phase Emulsion
Legal load has obtained the macropore macroscopic view absorption of surface fine structuring on the porous carrier that oiliness organic polymer forms
Agent, the size of the adsorbent can reach Centimeter Level to meter level, can not only efficiently catch metal ion and other pollutants, remove
Fall most of heavy metal ion in water, while can easily and effectively be separated from the water again, realize efficient absorption and simplicity
Separated combination, excellent combination property；
2) porous adsorbent made from will not cause new pollution, can be in neutral, alkalescent and weak acid when adsorbing heavy metal
Property under the conditions of carry out, the residual concentration of most heavy metals is at 0.05-25ppm grades after absorption；Can also be at the same time under the conditions of meta-alkalescence
Liquidity limit dyestuff and cationic surfactant, make its residual concentration be down to it is several arrive dozens of ppb, using wide
It is general；
3) preparation method of adsorbent is simple, suitable for large-scale production.
Brief description of the drawings
Fig. 1 is the SEM spectrograms for the adsorbent being prepared in embodiment 1.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1：
1) synthesis of tree-shaped two parent：
Poly- Ethylenimine (PEI, 1g) is taken, vacuum line processing half an hour is connected at 60 DEG C, to eliminate wherein adsorb two
Carbonoxide, then adds dimethylformamide (DMF, 50mL) dissolving.Finely ground KOH (2 amino equivalent) powder is added at room temperature
And stir, afterwards at 0 DEG C instill carbon disulfide (1.1 amino equivalent), continue stirring 3 it is small when and be gradually restored to room temperature, obtain
Reddish yellow color substance (PEI-DTC).
Add bromohexadecane base (0.3-0.5 amino equivalents), be warming up at 50-65 DEG C be kept stirring 5 it is small when.Add chlorine
Imitative and water, concussion are stood, and suitably plus sodium chloride makes oil-water-layer be layered completely.Oil reservoir is taken out, removes inorganic matter after sodium sulphate drying
And chloroform, obtain tree-shaped two parent.
2) preparation of adsorbent：
Take above-mentioned tree-shaped two parent (1g), 2-EHA (EHA, 4.8g), double polyalkylene glycol acrylate esters
(1.2g, wherein polyethylene glycol polymeric degree stir logical nitrogen below 4) to be dissolved in azodiisobutyronitrile (50mg) in toluene (3mL)
Water (40mL) is added dropwise in gas side.After concentrated emulsions are formed, it is transferred in beaker shape container, preservative film covering, in 65-75 DEG C of insulation
To curing.Take out, washed with ethanol afterwards.The porosity of mercury injection method measure block is 79%, and pore size is in 500nm to 50 μm of model
In enclosing, surface area 35m2/ g, is via material.The water absorption rate of the adsorbent is 2.65g/g, its SEM spectrogram is as shown in Figure 1.
20mL is taken to contain Cd2+、Cu2+、Pb2+、Co2+Nitrate (concentration of every kind of metal is 60ppm) water sample, to
Adsorbent 2g is wherein added, water sample is composed with inductance Induced Plasma and detected after standing 8 days, it turns out that Cd2+、Cu2+、Pb2+、Co2+
Concentration be respectively 0.63ppm, 0.05ppm, 0.56ppm and 9ppm.
Embodiment 2：
Bromo 16 is replaced with the ether capped dimethyl silicone polymer of single glycerine (molecular weight 5000,0.2 equivalent of amino)
Alkyl, remaining is the same as embodiment 1.Reaction forms white suspension, centrifuges to obtain tree-shaped two parent, and be equally used for porous material
The synthesis of adsorbent, the adsorbent of gained to the Scavenging activity of metal in error range it is consistent with embodiment 1.
Embodiment 3：
(bibliography Wan D.C, Yuan J.J., Pu are pressed with the ether capped polystyrene of single glycerine
H.T.Macromolecular Nancapsule Derived from Hyperbranched Polyethylenimine
(HPEI):Mechanism of Guest Encapsulation versus Molecular Parameters[J]
.Macromolecules.2009,42 (5), 1533-1540) synthesis, molecular weight 8000, dosage is 0.2 equivalent of amino) replace
The ether capped dimethyl silicone polymer of single glycerine, reacts two parents of synthesis, remaining is equally used for more with embodiment 2 with PEI-DTC
The synthesis of Porous materials adsorbent.Obtained adsorbent is similar with the adsorbent of embodiment 1 to the Scavenging activity of heavy metal.
The adsorbent can also be used for the dye of positive ion (methylene blue) and cationic surfactant (cetyl chloride
Pyridiniujm, CPC) absorption.100mL is taken to contain the emerald green orchid GB (10 of cation-7Mol/L water), cutting one piece of above-mentioned adsorbent, (1g is left
It is right) input, pH is adjusted to 11, magnetic force gentle agitation 9 days.Pull adsorbent out, water sample concentrates 100 times with freeze-drying, with purple
Outside-visible spectrometry detection.The result shows that the residual quantity of raw water sample Methylene Blue is 5ppb or so, the residual of CPC is about
12ppb。
Embodiment 4：
1) synthesis of tree-shaped two parent：
The ether capped polyphenyl second of glycerine is replaced with the ether capped polypropylene glycol of glycerine (molecular weight 2500,0.3 equivalent of amino)
Alkene, remaining synthesizes tree-shaped two parent with embodiment 3.
2) synthesis of polyurethane porous adsorbent.
A beaker shape container is taken, adds polycaprolactone glycol (5g, molecular weight 2000,2.5mmol), polypropylene oxide glycol
(5g, molecular weight 2500,2mmol), toluene (6mL), pMDI (2.5g, Yantai Wanhua Products) and above-mentioned tree-shaped two parent
(1.9g), and water (60mL) is added dropwise under vigorous stirring, dripped off in half an hour, obtain concentrated emulsions.A container separately is taken, liner is fresh-keeping
Film, sticky concentrated emulsions are poured into, and are stood hatching and are cured (about needing 12-24h).The block formed is taken out, is soaked with a large amount of ethanol
Adsorbent is obtained after washing.
The adsorbent is used for the absorption of heavy metal, and process is similar to embodiment 1.
Embodiment 5：
Adsorbent after absorption heavy metal in embodiment 4 to be pulled out, water is removed in extruding, then puts into acid water (pH=3),
When heating 2 is small at 50 DEG C.Pull out, put into again in alkalescence KOH/ carbon disulfide/water (0-25 DEG C), the use of carbon disulfide afterwards
Amount is about the 0.2% of adsorbent mass.PH to 7 or so is adjusted after when slightly concussion 5 is small, after pulling out, is fully washed with ethanol.The suction
Attached dose is re-used for metal adsorption, and the residual quantity of metal is suitable with embodiment 4.
Embodiment 6：
A kind of adsorbent of aminodithioformic acid functionalization, the adsorbent include porous carrier and are supported on porous load
Tree-shaped two parent on body, tree-shaped two parent are made of hydrophilic core and the oleophylic shell being coated on outside hydrophilic core, and hydrophilic core is
Poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, oleophylic shell are lipophilic cpd.
Wherein, porous carrier is formed by oiliness organic polymer, and oiliness organic matter is alkene.
Lipophilic cpd is more than 12 lipophilic molecules for carbon number, and lipophilic cpd is hexadecane.
It is connected directly between hydrophilic core and oleophylic shell.
The preparation method of the adsorbent be using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as point
Dephasing, forms concentrated emulsions, by radical polymerization, washing.
The adsorbent is in application, put into the water that pH value is 4, for adsorbing heavy metal ion.
Embodiment 7：
A kind of adsorbent of aminodithioformic acid functionalization, the adsorbent include porous carrier and are supported on porous load
Tree-shaped two parent on body, tree-shaped two parent are made of hydrophilic core and the oleophylic shell being coated on outside hydrophilic core, and hydrophilic core is
Poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, oleophylic shell are lipophilic cpd.
Wherein, porous carrier is formed by oiliness organic polymer, and oiliness organic matter is alkadienes.
Lipophilic cpd is more than 12 lipophilic molecules for carbon number, and lipophilic cpd is polystyrene.
It is connected between hydrophilic core and oleophylic shell by 2- hydroxyl trimethylene bases.
The preparation method of the adsorbent be using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as point
Dephasing, forms concentrated emulsions, by radical polymerization, washing.
The adsorbent is in application, put into the water that pH value is 11, for adsorbing heavy metal ion.
Embodiment 8：
A kind of adsorbent of aminodithioformic acid functionalization, the adsorbent include porous carrier and are supported on porous load
Tree-shaped two parent on body, tree-shaped two parent are made of hydrophilic core and the oleophylic shell being coated on outside hydrophilic core, and hydrophilic core is
Poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, oleophylic shell are lipophilic cpd.
Wherein, porous carrier is formed by oiliness organic polymer, and oiliness organic matter includes alkene and alkadienes.
Lipophilic cpd is more than 12 lipophilic molecules for carbon number, and lipophilic cpd is polysiloxanes.
It is connected directly between hydrophilic core and oleophylic shell.
The preparation method of the adsorbent be using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as point
Dephasing, forms concentrated emulsions, by radical polymerization, washing.
The adsorbent is in application, put into the water that pH value is 9, for adsorbing heavy metal ion.
Embodiment 9：
A kind of adsorbent of aminodithioformic acid functionalization, the adsorbent include porous carrier and are supported on porous load
Tree-shaped two parent on body, tree-shaped two parent are made of hydrophilic core and the oleophylic shell being coated on outside hydrophilic core, and hydrophilic core is
Poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, oleophylic shell are lipophilic cpd.
Wherein, porous carrier is formed by oiliness organic polymer, and oiliness organic matter includes crystallinity glycol, amorphism two
Alcohol and polyisocyanate, crystallinity glycol are esterdiol in poly- alkylene, and amorphism glycol is ployalkylene glycol.
Lipophilic cpd is more than 12 lipophilic molecules for carbon number, and lipophilic cpd is poly- (styrene-co- methyl
Acrylate).
It is connected between hydrophilic core and oleophylic shell by 2- hydroxyl trimethylene bases.
The preparation method of the adsorbent be using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as point
Dephasing, formed concentrated emulsions, by or polycondensation, washing.
The adsorbent is in application, put into the water that pH value is 6, for adsorbing heavy metal ion.
Embodiment 10：
A kind of adsorbent of aminodithioformic acid functionalization, the adsorbent include porous carrier and are supported on porous load
Tree-shaped two parent on body, tree-shaped two parent are made of hydrophilic core and the oleophylic shell being coated on outside hydrophilic core, and hydrophilic core is
Poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups, oleophylic shell are lipophilic cpd.
Wherein, porous carrier is formed by oiliness organic polymer, and oiliness organic matter includes crystallinity glycol, amorphism two
Alcohol and polyisocyanate, crystallinity glycol are esterdiol in poly- alkylene, and amorphism glycol is polydimethylsiloxanediols diols.
Lipophilic cpd is more than 12 lipophilic molecules for carbon number, and lipophilic cpd is polypropylene glycol.
It is connected directly between hydrophilic core and oleophylic shell.
The preparation method of the adsorbent be using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as point
Dephasing, forms concentrated emulsions, by polycondensation, washing.
The adsorbent is in application, put into the water that pH value is 8, for adsorbing heavy metal ion.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously easily can make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel disclose according to the present invention, do not depart from improvement that scope made and modification all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of adsorbent of aminodithioformic acid functionalization, it is characterised in that the adsorbent includes porous carrier and bears
Tree-shaped two parent on porous support is carried, tree-shaped two parent is by hydrophilic core and the oleophylic shell structure being coated on outside hydrophilic core
It is the poly- Ethylenimine with multiple aminodithioformic acid root anionic functional groups into, the hydrophilic core, the oleophylic
Shell is lipophilic cpd.
2. the adsorbent of a kind of aminodithioformic acid functionalization according to claim 1, it is characterised in that described is more
Hole carrier is formed by oiliness organic polymer.
A kind of 3. adsorbent of aminodithioformic acid functionalization according to claim 2, it is characterised in that the oil
Property organic matter includes one or both of alkene or alkadienes.
A kind of 4. adsorbent of aminodithioformic acid functionalization according to claim 2, it is characterised in that the oil
Property organic matter includes crystallinity glycol, amorphism glycol and polyisocyanate, and the crystallinity glycol is poly- alkylene lactone
Glycol, the amorphism glycol are ployalkylene glycol or polydimethylsiloxanediols diols.
A kind of 5. adsorbent of aminodithioformic acid functionalization according to claim 1, it is characterised in that the parent
Oil composition is more than 12 lipophilic molecules for carbon number.
A kind of 6. adsorbent of aminodithioformic acid functionalization according to claim 5, it is characterised in that the parent
Oil composition is hexadecane, polystyrene, polysiloxanes, poly- (styrene-co- methacrylates) or polypropylene glycol.
A kind of 7. adsorbent of aminodithioformic acid functionalization according to claim 1, it is characterised in that the parent
It is connected directly between water core and oleophylic shell or is connected by 2- hydroxyl trimethylene bases.
8. a kind of preparation method of such as adsorbent of claim 1 to 7 any one of them aminodithioformic acid functionalization, its
It is characterized in that, this method is using tree-shaped two parent as stabilizer, using oil phase as continuous phase, using water as dispersed phase, is formed dense
Lotion, by polymerization, washing, that is, obtains the adsorbent.
9. a kind of preparation method of the adsorbent of aminodithioformic acid functionalization according to claim 8, its feature exist
In described is polymerized to radical polymerization or polycondensation.
10. a kind of application of such as adsorbent of claim 1 to 7 any one of them aminodithioformic acid functionalization, it is special
Sign is, is in the water of 4-11, for adsorbing heavy metal ion by adsorbent input pH value.
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| CN109621918A (en) * | 2018-12-17 | 2019-04-16 | 同济大学 | A kind of amino functional porous material and its preparation method and application |
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| CN109621918A (en) * | 2018-12-17 | 2019-04-16 | 同济大学 | A kind of amino functional porous material and its preparation method and application |
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