CN106279534A - A kind of oxygen metal anion imprinted polymer and preparation method thereof - Google Patents
A kind of oxygen metal anion imprinted polymer and preparation method thereof Download PDFInfo
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- CN106279534A CN106279534A CN201610648720.8A CN201610648720A CN106279534A CN 106279534 A CN106279534 A CN 106279534A CN 201610648720 A CN201610648720 A CN 201610648720A CN 106279534 A CN106279534 A CN 106279534A
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- imprinted polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
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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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
Abstract
The invention provides the preparation method of a kind of oxygen metal anion imprinted polymer: nitrogen heterocycles function monomer and oxygen metal anion are dissolved, obtain monomer trace Ar ion mixing solution；Cross-linking agent and initiator are dissolved, obtains additive mixed solution；Under an inert atmosphere, described monomer trace Ar ion mixing solution and additive mixed solution are carried out precipitation, obtains comprising the imprinted polymer of oxygen metal anion；Comprise the oxygen metal anion in the imprinted polymer of oxygen metal anion described in sloughing, obtain oxygen metal anion imprinted polymer.The oxygen metal anion imprinted polymer that the present invention provides has the framing structure of porous, specific surface area is 434.04m2/g；Additionally, selectivity and stable circulation performance have promoted, further improve the absorption property of oxygen metal anion imprinted polymer, high adsorption capacity is up to 55mg/g.
Description
Technical field
The present invention relates to metal ion adsorption material technical field, particularly to a kind of oxygen metal anion trace polymerization
Thing and preparation method thereof.
Background technology
Heavy metal pollution is the persistent ailment of current environment pollution control, is also the focus of current international environmental studies
(M.S.Islam,M.K.Ahmed,M.Raknuzzaman,et al.,Ecol.Indic.,2015,48,282).Heavy metal enters
Easily by life entity enrichment, amplification, serious threat to human health and ecological environment after environment.
Heavy metal pollution is primarily present two types, and a class is with Cu2+、Pb2+、Zn2+Deng the heavy metal cation for representative
Pollute；Another kind of is the oxygen metal anion contamination with As, Sb, W, Cr etc. as representative.For Heavy Metals in Waters cation
Pollution treatment method numerous, most of method disclosure satisfy that the demand of qualified discharge and advanced treating, but to oxygen-containing
Anionic metal process the main removal concentrating oxygen containing As and Sb ion, to the concern of other oxygen metal anion with grind
Study carefully the fewest.
Based on the theoretical ion imprinted polymer (Ion Imprinted Polymers, IIPs) of lock & key because having and
The cavity of target molecular structure complementation and special adsorption site so that it is when selective absorption and recovery oxygen metal anion
There is incomparable advantage, be most to be expected to become the oxygen metal anionic pollutant degree of depth in water body to remove collaborative resource
New technique.But, the ion imprinted polymer provided in prior art is the most limited to the identification ability of oxygen metal anion.
Summary of the invention
It is an object of the invention to provide a kind of oxygen metal anion imprinted polymer and preparation method thereof, the present invention obtains
To oxygen metal anion imprinted polymer have excellence identification ability.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides the preparation method of a kind of oxygen metal anion imprinted polymer, comprise the steps:
Nitrogen heterocycles function monomer and oxygen metal anion are dissolved, obtains monomer-trace Ar ion mixing solution；
Cross-linking agent and initiator are dissolved, obtains additive mixed solution；
Under an inert atmosphere, described monomer-trace Ar ion mixing solution and additive mixed solution are carried out precipitation,
Obtain comprising the imprinted polymer of oxygen metal anion；
Comprise the oxygen metal anion in the imprinted polymer of oxygen metal anion described in sloughing, obtain oxygen metal
Anion imprinted polymer.
Preferably, described nitrogen heterocycles function monomer is tetrabormated two-4,5-bis-(di-2-ethylhexylphosphine oxide imidazoles) acridine and spreading out
One or more in biological, phthalocyanine and derivant, Porphyrin and its derivative and protoporphyrin and derivant thereof.
Preferably, the structural formula of described oxygen metal anion is XnOm -、XnOm 2-、XnOm 3-、HXnOm -Or XnOm 2-；
Wherein, n is 1,2,3 or 4；
M is 3,4,6,7 or 13；
X is Au, Ag, Cu, Si, Cr, Ti, Te, Se, V, As, Sb, W, Mo, U, Os, Nb, Bi, Pb, Co, Ni, Fe, Mn, Ru,
Re, Tc, Al or B.
Preferably, the ratio of the amount of the material of described nitrogen heterocycles function monomer and oxygen metal anion is (1～5): (1
～2).
Preferably, the temperature that described nitrogen heterocycles function monomer and oxygen metal anion are dissolved is 20～40 DEG C；
The time that described nitrogen heterocycles function monomer and oxygen metal anion are dissolved is 30～120min.
Preferably, the ratio of the amount of the material of described nitrogen heterocycles function monomer and cross-linking agent is (1～5): (4～30).
Preferably, the amount of the material of described initiator is the amount sum of nitrogen heterocycles function monomer and crosslinker species
0.5～5%.
Preferably, the temperature of described precipitation is 50～90 DEG C；
The time of described precipitation is 12～48 hours.
Present invention also offers a kind of oxygen metal anion imprinted polymer, be made up of nitrogen heterocycles function monomer, with
Oxygen metal anion is template ion.
Preferably, described nitrogen heterocycles function monomer is tetrabormated two-4,5-bis-(di-2-ethylhexylphosphine oxide imidazoles) acridine and spreading out
One or more in biological, phthalocyanine and derivant, Porphyrin and its derivative and protoporphyrin and derivant thereof.
The invention provides the preparation method of a kind of oxygen metal anion imprinted polymer, comprise the steps: nitrogen
Heterocyclic function monomer and oxygen metal anion are dissolved, and obtain monomer-trace Ar ion mixing solution；By cross-linking agent and initiator
Dissolve, obtain additive mixed solution；Under an inert atmosphere, described monomer-trace Ar ion mixing solution and additive are mixed
Solution carries out precipitation, obtains comprising the imprinted polymer of oxygen metal anion；Comprise described in sloughing oxygen metal cloudy from
Oxygen metal anion in the imprinted polymer of son, obtains oxygen metal anion imprinted polymer.
The oxygen metal anion imprinted polymer that the present invention provides, with azacyclo-as function monomer, utilizes in single macro ring
The N-H A in many sites-Interaction force, has good selective absorption to anion；π-π the double bond of macro ring is piled up
The structure of effect, improves the specific surface area of material, decreases resistance to mass tranfer so that the imprinted polymer of preparation has porous knot
Structure.Additionally, due to the existence of cyclic ligand, it is to avoid the eluting of function monomer, function monomer is without introducing double bond.Experimental result
Showing, the oxygen metal anion imprinted polymer that the present invention provides has the framing structure of porous, specific surface area is
434.04m2/g；Additionally, the interference free performance of the oxygen metal anion imprinted polymer of present invention offer and cyclical stability
Can promote, further improve the absorption property of oxygen metal anion imprinted polymer, high adsorption capacity up to
55mg/g。
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that the embodiment of the present invention 1 prepares oxygen metal anion imprinted polymer；
Fig. 2 is the scanning electron microscopy of the oxygen metal anion imprinted polymer that the embodiment of the present invention 1 obtains；
Fig. 3 is the scanning electron microscopy of the nonionic imprinted polymer that comparative example 1 of the present invention obtains；
Fig. 4 is the nitrogen adsorption-desorption curve of the oxygen metal anion imprinted polymer that the embodiment of the present invention 1 obtains；
The nonionic that Fig. 5 is the oxygen metal anion imprinted polymer that obtains of the embodiment of the present invention 1 and comparative example 1 obtains
The static adsorption figure of imprinted polymer；
The nonionic that Fig. 6 is the oxygen metal anion imprinted polymer that obtains of the embodiment of the present invention 1 and comparative example 1 obtains
The adsorptive selectivity energy of adsorption of imprinted polymer is tried hard to；
Fig. 7 is the stable circulation performance figure of the oxygen metal anion imprinted polymer that the embodiment of the present invention 1 obtains.
Detailed description of the invention
The invention provides the preparation method of a kind of oxygen metal anion imprinted polymer, comprise the steps:
Nitrogen heterocycles function monomer and oxygen metal anion are dissolved, obtains monomer-trace Ar ion mixing solution；
Cross-linking agent and initiator are dissolved, obtains additive mixed solution；
Under an inert atmosphere, described monomer-trace Ar ion mixing solution and additive mixed solution are carried out precipitation,
Obtain comprising the imprinted polymer of oxygen metal anion；
Comprise the oxygen metal anion in the imprinted polymer of oxygen metal anion described in sloughing, obtain oxygen metal
Anion imprinted polymer.
Nitrogen heterocycles function monomer and oxygen metal anion are dissolved by the present invention, obtain monomer-trace Ar ion mixing molten
Liquid.Nitrogen heterocycles function monomer and oxygen metal anion are preferably dissolved in the middle of the first solvent by the present invention.In the present invention,
Described nitrogen heterocycles function monomer be preferably tetrabormated two-4,5-two (di-2-ethylhexylphosphine oxide imidazoles) acridine and derivant thereof, phthalocyanine and
One or more in its derivant, Porphyrin and its derivative and protoporphyrin and derivant thereof.
In the present invention, the structural formula of described oxygen metal anion is preferably XnOm -、XnOm 2-、XnOm 3-、HXnOm -Or
XnOm 2-；
Wherein, n is 1,2,3 or 4；
M is 3,4,6,7 or 13；
X is Au, Ag, Cu, Si, Cr, Ti, Te, Se, V, As, Sb, W, Mo, U, Os, Nb, Bi, Pb, Co, Ni, Fe, Mn, Ru,
Re, Tc, Al or B.
The currently preferred form with the compound of described oxygen metal anion adds described oxygen metal anion.
Add sodium arsenite, 12 water natrium arsenicums or antimony potassium tartrate trihydrate concrete in the embodiment of the present invention provide correspondence
Oxygen metal anion.
In the present invention, the ratio of the amount of the material of described nitrogen heterocycles function monomer and oxygen metal anion is preferably (1
～5): (1～2), more preferably (2～4): (1～2), most preferably 3:(1～2).
In the present invention, described first solvent is preferably toluene, oxolane, dimethyl sulfoxide, N, N-dimethyl formyl
Amine, acetonitrile, dichloroethanes, chloroform, Hexalin, 2-methyl cellosolve, isopropanol, ethanol, one or more in first alcohol and water.
In the present invention, the amount of the material of described nitrogen heterocycles function monomer and the volume ratio of the first solvent are preferably (0.1～0.5)
Mmol:(10～20) mL, more preferably (0.2～0.4) mmol:(12～18) mL, most preferably 0.3mmol:(14～16) mL.
In the present invention, the temperature that described nitrogen heterocycles function monomer and oxygen metal anion are dissolved is preferably 20～40
DEG C, more preferably 25～35 DEG C, most preferably 28～33 DEG C；Described nitrogen heterocycles function monomer and oxygen metal anion are dissolved
Time be preferably 30～120min, more preferably 50～100min, most preferably 60～80min.
In the present invention, described nitrogen heterocycles function monomer and oxygen metal anion are dissolved the most under agitation
Carrying out, described stirring is preferably magnetic agitation.In the present invention, the speed of described magnetic agitation is preferably 100～400rmp, more
It is preferably 150～350rmp, most preferably 200～300rmp.
Cross-linking agent and initiator are dissolved by the present invention, obtain additive mixed solution.The present invention is preferably by cross-linking agent, initiation
Agent is dissolved in the second solvent.In the present invention, described cross-linking agent be preferably trimethacrylate acid trihydroxy methyl propyl ester (TRIM),
Ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB) or N, N'-methylene-bisacrylamide (MBA).At this
In invention, the ratio of the amount of the material of described nitrogen heterocycles function monomer and cross-linking agent is preferably (1～5): (4～30), more preferably
For (2～4): (10～25), most preferably 3:(15～20).
In the present invention, described initiator preferably azo type free radical initiator and/or peroxide free radical draw
Send out one or more in agent, more preferably azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), potassium peroxydisulfate and benzoyl peroxide.
In the present invention, the amount of the material of described initiator is preferably the nitrogen heterocycles function monomer amount sum with crosslinker species
0.5～5%, more preferably 1～4%, most preferably 2～3%.
In the present invention, described second solvent is preferably toluene, oxolane, dimethyl sulfoxide, N, N-dimethyl formyl
Amine, acetonitrile, dichloroethanes, chloroform, Hexalin, 2-methyl cellosolve, isopropanol, ethanol, one or more in first alcohol and water.
In the present invention, the amount of the material of described cross-linking agent and the volume ratio of the second solvent are preferably (0.4～3) mmol:(5～15)
ML, more preferably (1～2.5) mmol:(8～13) mL, most preferably (1.5～2) mmol:(10～12) mL.
After obtaining described monomer-trace Ar ion mixing solution and additive mixed solution, the present invention under an inert atmosphere,
Described monomer-trace Ar ion mixing solution and additive mixed solution are carried out precipitation, obtain comprising oxygen metal cloudy from
The imprinted polymer of son.The present invention does not has particular/special requirement to described inert atmosphere, and concrete can be nitrogen and/or argon.This
Invention, preferably before described precipitation, is passed through noble gas, to remove oxygen in reaction system.In the present invention, described
The time removing oxygen is preferably 10～60min, more preferably 20～50min, most preferably 30～40min.
The present invention does not has special wanting to the order by merging of described monomer-trace Ar ion mixing solution and additive mixed solution
Asking, additive mixed solution is preferably joined in monomer-trace Ar ion mixing solution by the present invention.In the present invention, described heavy
The temperature reacted of forming sediment is preferably 50～90 DEG C, more preferably 60～80 DEG C, most preferably 65～75 DEG C；Described precipitation time
Between be preferably 12～48 hours, more preferably 15～40 hours, most preferably 20～30 hours.
In the present invention, described precipitation is carried out the most under agitation, and described stirring is preferably magnetic agitation.?
In the present invention, the speed of described magnetic agitation is preferably 300～500rmp, more preferably 350～450rmp, and most preferably 380
～430rmp.
After the imprinted polymer comprising oxygen metal anion described in obtaining, the present invention slough described in comprise oxygen metal
Oxygen metal anion in the imprinted polymer of anion, obtains oxygen metal anion imprinted polymer.
The present invention does not has particular/special requirement to the concrete operations of described removing oxygen metal anion, uses people in the art
Template ion removal methods known to Yuan carries out removing.In the present invention, described removal methods comprises the most successively
Three processes are washed, clean and be vacuum dried to alcohol.
In the present invention, the eluent that described alcohol is washed is preferably methanol aqueous solution；Water and methanol in described methanol aqueous solution
Volume ratio be preferably 1:(1～10), more preferably 1:(2～8), most preferably 1:(4～6).In the present invention, described alcohol is washed
Number of times be preferably 1～5 time, concrete can be 1 time, 2 times, 3 times, 4 times or 5 times.
In the present invention, the one during the eluent of described cleaning is preferably ammonia, methanol solution and sodium hydroxide solution
Or it is several.In the present invention, the concentration of described eluent is preferably 0.1～2mol/L, more preferably 0.5～1.5mol/L,
It is preferably 0.8～1.3mol/L.In the present invention, the number of times that described eluent cleans is preferably 1～5 time, and concrete can be 1
Secondary, 2 times, 3 times, 4 times or 5 times.
The material obtained, preferably after described cleaning, is washed by the present invention.Described washing is not appointed by the present invention
What particular/special requirement, it is possible to the matter detergent described cleaning obtained is to neutral.
In the present invention, described vacuum drying temperature is preferably 40～80 DEG C, more preferably 50～70 DEG C, most preferably
55～65 DEG C；Described vacuum drying vacuum is preferably 0.06～0.08MPa, more preferably 0.065～0.075MPa, optimum
Elect 0.068～0.073MPa as.The present invention does not has particular/special requirement to the described vacuum drying time, is dried to constant weight.
Present invention also offers a kind of oxygen metal anion imprinted polymer, be made up of nitrogen heterocycles function monomer, with
Oxygen metal anion is template ion.
In the present invention, described nitrogen heterocycles function monomer is preferably tetrabormated two-4,5-bis-(di-2-ethylhexylphosphine oxide imidazoles) a word used for translation
One or more in pyridine and derivant, phthalocyanine and derivant thereof, Porphyrin and its derivative and protoporphyrin and derivant thereof.
The invention provides the preparation method of a kind of oxygen metal anion imprinted polymer, comprise the steps: nitrogen
Heterocyclic function monomer and oxygen metal anion are dissolved, and obtain monomer-trace Ar ion mixing solution；By cross-linking agent and initiator
Dissolve, obtain additive mixed solution；Under an inert atmosphere, described monomer-trace Ar ion mixing solution and additive are mixed
Solution carries out precipitation, obtains comprising the imprinted polymer of oxygen metal anion；Comprise described in sloughing oxygen metal cloudy from
Oxygen metal anion in the imprinted polymer of son, obtains oxygen metal anion imprinted polymer.
The oxygen metal anion imprinted polymer that the present invention provides, with azacyclo-as function monomer, utilizes in single macro ring
The N-H A in many sites-Interaction force, has good selective absorption to anion；π-π the double bond of macro ring is piled up
The structure of effect, improves the specific surface area of material, decreases resistance to mass tranfer so that the imprinted polymer of preparation has porous knot
Structure.Additionally, due to the existence of cyclic ligand, it is to avoid the eluting of function monomer, function monomer is without introducing double bond.Experimental result
Showing, the oxygen metal anion imprinted polymer that the present invention provides has the framing structure of porous, specific surface area is
434.04m2/g；Additionally, the selectivity of the oxygen metal anion imprinted polymer of present invention offer and stable circulation performance are equal
Having promoted, further improve the absorption property of oxygen metal anion imprinted polymer, high adsorption capacity is up to 55mg/
g。
Carry out below in conjunction with oxygen metal anion imprinted polymer that the present invention is provided by embodiment and preparation method thereof
Detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
0.25g tetrabormated two-4,5-two (di-2-ethylhexylphosphine oxide imidazoles) acridine and 0.065g sodium arsenite are dissolved in 10ml diformazan
In base sulfoxide solvent, it is heated to 40 DEG C, with the speed magnetic agitation 1 hour of 400rmp, obtains mixed solution A.
0.5ml ethylene glycol dimethacrylate (EGDMA) and 30mg azodiisobutyronitrile is dissolved with 10ml methanol
(AIBN) mixed solution B, is obtained.
Mixed solution B is added in mixed solution A, is passed through nitrogen 15 minutes, after being warming up to 70 DEG C, with the speed of 500rmp
Magnetic agitation is reacted 12 hours, obtains faint yellow solid precipitate.With deionized water and methanol cyclic washing product, to remove it
Organic substance on surface；Then with the sodium hydroxide solution of 0.5mol/L, the template ion in ion imprinted polymer is washed completely
Go out, 65 DEG C, be vacuum dried 12h under the conditions of 0.08MPa, obtain oxygen metal anion imprinted polymer.
The present embodiment prepares the schematic flow sheet of oxygen metal anion imprinted polymer as it is shown in figure 1, Fig. 1 is the present invention
Embodiment 1 prepares the schematic flow sheet of oxygen metal anion imprinted polymer.
Comparative example 1
The preparation of nonionic imprinted polymer: with the preparation method of embodiment 1 oxygen metal anion imprinted polymer, only
One is distinguished as without template ion: oxygen metal anion.
The embodiment of the present invention 1 and comparative example 1 obtain the scanned picture of product the most as shown in Figures 2 and 3, and wherein, Fig. 2 is this
The scanning electron microscopy of the oxygen metal anion imprinted polymer that inventive embodiments 1 obtains, Fig. 3 is comparative example 1 of the present invention
The scanning electron microscopy of the nonionic imprinted polymer obtained.From Fig. 2 and Fig. 3, synthesize with nitrogen heterocycles function monomer
Imprinted polymer be respectively provided with the framing structure of porous.
The embodiment of the present invention 1 obtains the nitrogen adsorption-desorption curve of product as shown in Figure 4, and Fig. 4 is the embodiment of the present invention 1
Nitrogen adsorption-the desorption curve of the oxygen metal anion imprinted polymer obtained.As shown in Figure 4, what the present invention provided is oxygen-containing
Anionic metal imprinted polymer has good absorption property to nitrogen.Obtain additionally, analyze, the oxygen-containing gold that the present invention provides
The specific surface area belonging to anion imprinted polymer is 434.04m2/g.Prove that nitrogen heterocycles function monomer contributes to imprinted polymer
The raising of material specific surface area, and specific surface area improves the further improvement contributing to absorption property.
The static adsorption result of the embodiment of the present invention 1 and comparative example 1 product is as it is shown in figure 5, Fig. 5 is the embodiment of the present invention 1
To oxygen metal anion imprinted polymer and the static adsorption figure of nonionic imprinted polymer that obtains of comparative example 1.By Fig. 5
Understanding, the oxygen metal anion imprinted polymer that the embodiment of the present invention 1 obtains has the absorbability of excellence, high adsorption capacity
Up to 55mg/g, imprinting factor reaches 2.16.
Embodiment 1 and comparative example 1 are obtained product and are placed in containing AsO by the present invention3 3-、Cl-、SO4 2-、HPO4 2-、NO3 -With
Mo7O24 6-Adsorbent solution in carry out template ion select performance test, select performance as shown in Figure 6, Fig. 6 is that the present invention implements
Oxygen metal anion imprinted polymer that example 1 obtains and the adsorptive selectivity of the nonionic imprinted polymer that comparative example 1 obtains
Energy of adsorption is tried hard to.It will be appreciated from fig. 6 that the oxygen metal anion imprinted polymer that the embodiment of the present invention 1 obtains is to AsO3 3-Selection
Property absorption property is the best.
The oxygen metal anion imprinted polymer that embodiment 1 is obtained by the present invention is placed in containing AsO3 3-Water body in enter
Row stable circulation performance is tested, and described oxygen metal anion imprinted polymer carries out adsorption-desorption operation five times repeatedly, surely
Qualitative energy is as it is shown in fig. 7, the cyclical stability of oxygen metal anion imprinted polymer that Fig. 7 is the embodiment of the present invention 1 to be obtained
Can figure.According to the result of Fig. 7, after 5 times are reused, the absorbability of oxygen metal anion imprinted polymer is only
Have dropped 9.78%, there is good stability and regeneration ability.
Knowable to above-mentioned experimental result, the oxygen metal anion imprinted polymer that the present embodiment provides has the bone of porous
Shelf structure, specific surface area are 434.04m2/g；Additionally, the anti-of oxygen metal anion imprinted polymer that the present embodiment provides is done
Immunity can promote with stable circulation performance, further improves the adsorptivity of oxygen metal anion imprinted polymer
Energy.
Embodiment 2
By molten to 0.25g tetrabormated two-4,5-two (di-2-ethylhexylphosphine oxide imidazoles) acridine and 0.079g antimony potassium tartrate trihydrate
In 10ml dimethyl sulfoxide solvent, it is heated to 40 DEG C, with the speed magnetic agitation 1 hour of 100rmp, obtains mixed solution A.
0.5ml ethylene glycol dimethacrylate (EGDMA) and 30mg azodiisobutyronitrile is dissolved with 10ml methanol
(AIBN) mixed solution B, is obtained.
Mixed solution B is added in mixed solution A, is passed through nitrogen 30 minutes, after being warming up to 70 DEG C, with the speed of 200rmp
Magnetic agitation is reacted 24 hours, obtains faint yellow solid precipitate.With deionized water and methanol cyclic washing product, to remove it
Organic substance on surface；Then with the sodium hydroxide solution of 0.5mol/L, the template ion in ion imprinted polymer is washed completely
Go out, 65 DEG C, be vacuum dried 12h under the conditions of 0.08MPa, obtain oxygen metal anion imprinted polymer.
According to the mode in embodiment 1, structure, specific surface area, selectivity and the cyclical stability of the present embodiment product are entered
Having gone detection, testing result is consistent with the result of embodiment 1.
Embodiment 3
0.25g tetrabormated two-4,5-two (di-2-ethylhexylphosphine oxide imidazoles) acridine and 0.165g 12 water natrium arsenicum are dissolved in 10ml
In acetonitrile solvent, it is heated to 30 DEG C, with the speed magnetic agitation 1 hour of 300rmp, obtains mixed solution A.
0.5ml ethylene glycol dimethacrylate (EGDMA) and 30mg azodiisobutyronitrile is dissolved with 10ml methanol
(AIBN) mixed solution B, is obtained.
Mixed solution B is added in mixed solution A, is passed through nitrogen 30 minutes, after being warming up to 70 DEG C, with the speed of 300rmp
Magnetic agitation is reacted 24 hours, obtains faint yellow solid precipitate.With deionized water and methanol cyclic washing product, to remove it
Organic substance on surface；Then with the sodium hydroxide solution of 0.25mol/L complete for the template ion in ion imprinted polymer
Wash out, 60 DEG C, be vacuum dried 12h under the conditions of 0.08MPa, obtain oxygen metal anion imprinted polymer.
According to the mode in embodiment 1, structure, specific surface area, selectivity and the cyclical stability of the present embodiment product are entered
Having gone detection, testing result is consistent with the result of embodiment 1.
Embodiment 4
0.281g protoporphyrin and 0.065g sodium arsenite are dissolved in 15ml methanol solvate, are heated to 30 DEG C, with 300rmp
Speed magnetic agitation 1 hour, obtain mixed solution A.
0.75ml ethylene glycol dimethacrylate (EGDMA) and 30mg azodiisobutyronitrile is dissolved with 10ml acetonitrile
(AIBN) mixed solution B, is obtained.
Mixed solution B is added in mixed solution A, is passed through nitrogen 30 minutes, after being warming up to 70 DEG C, with the speed of 300rmp
Magnetic agitation is reacted 24 hours, obtains faint yellow solid precipitate.With deionized water and methanol cyclic washing product, to remove it
Organic substance on surface；Then with the ammonia spirit of 0.5mol/L, the template ion in ion imprinted polymer is washed out completely,
60 DEG C, be vacuum dried 12h under the conditions of 0.08MPa, obtain oxygen metal anion imprinted polymer.
According to the mode in embodiment 1, structure, specific surface area, selectivity and the cyclical stability of the present embodiment product are entered
Having gone detection, testing result is consistent with the result of embodiment 1.
From above example result, the oxygen metal anion imprinted polymer that the present invention provides with nitrogen heterocyclic ring is
Function monomer, utilizes the N-H A in many sites in single macro ring-Interaction force, has good selectivity to anion
Absorption；The structure of the π-π double bond sedimentation of macro ring, improves the specific surface area of material, decreases resistance to mass tranfer so that preparation
Imprinted polymer there is loose structure.Additionally, due to the existence of cyclic ligand, it is to avoid the eluting of function monomer, function list
Body is without introducing double bond.Test result indicate that, the oxygen metal anion imprinted polymer that the present invention provides has the bone of porous
Shelf structure, specific surface area are 434.04m2/g；Additionally, the oxygen metal anion imprinted polymer of present invention offer is anti-interference
Performance and stable circulation performance have promoted, and further improve the adsorptivity of oxygen metal anion imprinted polymer
Can, high adsorption capacity is up to 55mg/g.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a preparation method for oxygen metal anion imprinted polymer, comprises the steps:
Nitrogen heterocycles function monomer and oxygen metal anion are dissolved, obtains monomer-trace Ar ion mixing solution；
Cross-linking agent and initiator are dissolved, obtains additive mixed solution；
Under an inert atmosphere, described monomer-trace Ar ion mixing solution and additive mixed solution are carried out precipitation, obtains
Comprise the imprinted polymer of oxygen metal anion；
Comprise the oxygen metal anion in the imprinted polymer of oxygen metal anion described in sloughing, obtain oxygen metal cloudy from
Sub-imprinted polymer.
Preparation method the most according to claim 1, it is characterised in that described nitrogen heterocycles function monomer be tetrabormated two-
4,5-bis-(di-2-ethylhexylphosphine oxide imidazoles) acridine and derivant, phthalocyanine and derivant thereof, Porphyrin and its derivative and protoporphyrin and
One or more in derivant.
Preparation method the most according to claim 1, it is characterised in that the structural formula of described oxygen metal anion is
XnOm -、XnOm 2-、XnOm 3-、HXnOm -Or XnOm 2-；
Wherein, n is 1,2,3 or 4；
M is 3,4,6,7 or 13；
X is Au, Ag, Cu, Si, Cr, Ti, Te, Se, V, As, Sb, W, Mo, U, Os, Nb, Bi, Pb, Co, Ni, Fe, Mn, Ru, Re,
Tc, Al or B.
Preparation method the most according to claim 1, it is characterised in that described nitrogen heterocycles function monomer and oxygen metal are cloudy
The ratio of the amount of the material of ion is (1～5): (1～2).
5. according to the preparation method described in Claims 1 to 4 any one, it is characterised in that described nitrogen heterocycles function monomer
The temperature dissolved with oxygen metal anion is 20～40 DEG C；
The time that described nitrogen heterocycles function monomer and oxygen metal anion are dissolved is 30～120min.
Preparation method the most according to claim 1, it is characterised in that described nitrogen heterocycles function monomer and the thing of cross-linking agent
The ratio of the amount of matter is (1～5): (4～30).
Preparation method the most according to claim 1, it is characterised in that the amount of the material of described initiator is nitrogen heterocycles merit
The 0.5～5% of the amount sum of energy monomer and crosslinker species.
8. according to the preparation method described in claim 6 or 7, it is characterised in that the temperature of described precipitation is 50～90 DEG C；
The time of described precipitation is 12～48 hours.
9. an oxygen metal anion imprinted polymer, it is characterised in that be made up of nitrogen heterocycles function monomer, with oxygen-containing gold
Genus anion is template ion.
Imprinted polymer the most according to claim 9, it is characterised in that described nitrogen heterocycles function monomer is tetrabormated
Two-4,5-two (di-2-ethylhexylphosphine oxide imidazoles) acridines and derivant, phthalocyanine and derivant thereof, Porphyrin and its derivative and protoporphyrin and
One or more in its derivant.
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| US6251280B1 (en) * | 1999-09-15 | 2001-06-26 | University Of Tennessee Research Corporation | Imprint-coating synthesis of selective functionalized ordered mesoporous sorbents for separation and sensors |
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