CN1886189A - Synthesis of ion imprinted polymer particles - Google Patents
Synthesis of ion imprinted polymer particles Download PDFInfo
- Publication number
- CN1886189A CN1886189A CNA2003801109410A CN200380110941A CN1886189A CN 1886189 A CN1886189 A CN 1886189A CN A2003801109410 A CNA2003801109410 A CN A2003801109410A CN 200380110941 A CN200380110941 A CN 200380110941A CN 1886189 A CN1886189 A CN 1886189A
- Authority
- CN
- China
- Prior art keywords
- ion
- erbium
- polymerization
- imprinted polymer
- function
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 239000002245 particle Substances 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 48
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 36
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- 238000002360 preparation method Methods 0.000 claims description 16
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 15
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
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- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 9
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- 238000010189 synthetic method Methods 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
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- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 2
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
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- HNUFDBQIXGQAEX-UHFFFAOYSA-N 2-chloroquinolin-8-ol Chemical class C1=C(Cl)N=C2C(O)=CC=CC2=C1 HNUFDBQIXGQAEX-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
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- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 1
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- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
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- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
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Abstract
Ion imprinted polymer materials are synthesized containing metal ion recognition sites. These particles are synthesized by copolymerizing with functional and cross linking monomers in presence of at least one imprint metal ion in the form of ternary complex. The polymerization was carried out by gamma-irradiation (in the absence of initiator) or photochemical and thermal polymerization (in presence of initiator, AIBN). These materials were ground and sieved after drying to obtain erbium ion imprinted polymer particles. The erbium ion was removed from the polymer particles by leaching with mineral acid which leaves cavities/binding sites in the polymer particles. The resultant polymer particles can be used as solid phase extractants for selective enrichment of erbium ions from dilute aqueous solutions.
Description
Invention field
The present invention relates to be used for the synthetic and method of the ion imprinted polymer particle of solid phase extractions pre-concentration erbium ion.Ion imprinted polymer particle prepares by radiochemistry polymerization, photochemical polymerization and heat polymerization.
Background of invention
Handle the rare earth-iron-boron part that monazite produces slight, moderate and severe by a series of beneficiation method.Last part contains 55-60%Y
2O
3With impurity Dy, Gd and Er.Preparation 99.9-99.999%Y
2O
3Importance be that it is widely used in the manufacturing of laser, superconductor and colour televistion phosphor.Therefore, being separated into of Dy, Gd and Er prepares so highly purified Y
2O
3The prerequisite of necessity.Three kinds of different polymerization processes describing in this patent can realize that erbium is from Y
2O
3The middle separation.
Enantiomer splits
Referenced patent application WO 98/07671; 1998, people such as Mark prepare compound brufen, naproxen and the Ketoprofen that imprinted polymer is used for the dissociated optical activity, obtain its enantiomer separately.With reference to United States Patent (USP) the 6th, 316, No. 235; 2O01, people such as Mosbach pass through at least a microsphere and at least a magnetosensitive composition, and one or more function monomers of copolymerization and cross-linking monomer prepared the magnetosensitive composition under for example iron oxide or nickel oxide existed.Remove microsphere subsequently, form the molecular memory recognition site.These particles are used for optionally separating two kinds of different enantiomeric forms.In addition with reference to United States Patent (USP) the 5th, 786, No. 427; 1998, people such as Arnold prepare the solid phase extractions material that comprises the polymer substrate that contains one or more metal complexs by molecular engram, optionally an a kind of enantiomer in conjunction with optically active amino acid or peptide.With reference to United States Patent (USP) the 5th, 461, No. 175; 1995, people such as Fischer have synthesized the chiral chromatogram material of the enantiomer that is used to separate the aryloxy propanol amine derivative.
Sensor
With reference to United States Patent (USP) the 6th, 063, No. 637; 2000, people such as Arnold have developed the sensor of being made up of metal complex, this metal complex can binding target molecule and is discharged proton, perhaps contains tradable part, and this commutative part is the exchange target molecule in the process of metal complex and target molecule combination.These sensors are used for detecting the existence of the analyte of sugar and other metal combinations.With reference to United States Patent (USP) the 5th, 587, No. 273; 1996, people such as Yan prepare molecular engram substrate and sensor by at first forming solution, the polymeric material that this solution comprises solvent and (a) can carry out addition reaction with nitrene, (b) crosslinking agent, (c) function monomer and (d) microsphere.Other application of molecular engram
With reference to United States Patent (USP) the 6th, 310, No. 110; 2001, people such as Markowitz by certainly the combination the similar thing synthetic molecules of surfactant trace loose structure to generate at least a supramolecular structure that contains exposed trace group.By in mixture, adding reactive monomeric, and allow these monomers and supramolecular structure polymerization, form the trace loose structure as template.With reference to United States Patent (USP) the 6th, 057, No. 377; 2000, people such as Sasaki have developed the method that forms molecular engram metal oxide sol-gel rubber material by molecular engram in surface, solvent and the microsphere of sol-gel material.With reference to United States Patent (USP) the 6th, 255, No. 461; 2003, Mosbach and Olof prepare the man-made antibody by molecular engram, and wherein methacrylic acid, ethylene glycol dimethacrylate and corticoid microsphere are in conjunction with forming the man-made antibody.These antibody can be used for separating and analytic process.References to U.S. patent application 2003-049970 number, 2003, people such as Magnus have prepared the selective absorbent that can be used for purifying or analyze large biological molecule.
Ion blotting-anion
With reference to U.S. Patent application 2003-113234 number, 2003, Murray has prepared molecular imprinted polymer membrane, is used for optionally collecting phosphate radical, nitrate anion and iron ion.The preparation of these films is by matrix monomer, cross-linking monomer, ion blotting complex, bleeding agent and polymerization initiator copolyreaction, removes ion and bleeding agent in the ion blotting complex subsequently.Bleeding agent produces passage on film, make film to communicate with the outer surface of film intermediate ion binding site.In U.S. Patent application 2003-059346 number, 2003, Murray mentions and utilizes the selectively penetrating polymer film to remove phosphate radical, nitrate anion.By iron ion imprinted preparation selective binding position.The polyester that combines with metal ion by utilization improves permeability; And polyester is removed from film by the acid treatment method identical with removing iron ion.Polyester produces passage guiding ion and moves to the trace position, has therefore improved flow and has kept selectivity.
Ion blotting-cation
With reference to United States Patent (USP) the 6th, 248, No. 842; 2001, people such as Singh are by replacing the chelate polymer that the aliphatic chelating agent produces selective crosslinking with polymerisable functional group.Then the aliphatic chelating agent of the replacement that will obtain and target metal ion, for example copper carries out complexation reaction.Add crosslinkable monomer again, with the complex material cross-linking reaction.The metal ion of coordination is removed, and having generated with the target metal ion is the cross-linked polymeric chelating agent of template.Referenced patent application WO99/15707 number; 1999, people such as John survey and extract the Uranyl ion by the polymer trace, but form or the COOH or the PhCOOH for molecular formula CTCOOH, its methyl and halogen replacement of coordination function are wherein arranged, and wherein T is hydrogen or any halogen (preferred chlorine).Gladis and Rao also propose the synthetic of ion imprinted polymer that solid phase extractions pre-concentration in the main body of tetravalence, trivalent and divalence inorganic ions from sea water solution and artificial seawater solution/separate Uranyl ion uses.Under the condition as function monomer and cross-linking monomer existence, synthesize the ternary mixed ligand coordination compound of trace ion and oxine (quinoline-8-ol) or its dihalo derivative and 4-vinylpridine at styrene and divinylbenzene.With reference to United States Patent (USP) the 6th, 251, No. 280,2001, people such as Dai adopt the ion blotting technology, utilize double function ligand such as amine, mercaptan, carboxylic acid, sulfonic acid and phosphoric acid to separate inorganic matter, the sorbent material of preparation mesopore.When formation is exclusively used in the mesopore sorbent material of erbium template ion, use the carboxylic acid group on the double function ligand.
People such as Rao are [referring to Trends in Anal.Chem.; 2003] commented ion imprinted polymer (IIP-SPE), prepared the adaptation material that is used for pre-concentration/separating metal by being used for solid phase extractions.Ion imprinted polymer (IIP) material with nano-pore is by forming the ternary complex of palladium trace ion and dimethyl glyoxime and 4-vinylpridine, and 2, under the existence of 2 '-azodiisobutyronitrile, with the cyclohexanol is pore former (porogen), with styrene and the hot copolymerization of divinylbenzene prepare [referring to people such as Sobhi, Anal.Chim.Acta, 488 (2003) 173-182].Prepared based on diethylene-triamine pentaacetic acid (DTPA) derivative, be used to separate the cation trace SPE material of La and Gd.In the presence of Gd salt the preparation material can observe the trace effect, and with corresponding blank polymer phase ratio, demonstrate high efficiency and high selectivity [referring to people such as Garcia, Tetrahedron Lett., 39 (1998) 8651].At Gd
3+Salt exists down, the functionalization monomer of DTPA and the commercial divinylbenzene copolyreaction of buying that contains 45% ethyl styrene.Find that resulting IIP has higher selectivity [referring to people such as Vigneau, Anal.Chim.Acta, 435 (2001) 75] to Gd comparison La.These selectivity researchs are also prolonged the Shen to utilizing Gd trace IIP to measure S
Gd/EuAnd S
Gd/Lu[referring to people such as Logneau, Chem.Lett. (2002) 202].People such as Biju [referring to Anal.Chim.Acta, 478 (2003) 43-51] by at DVB as in the presence of the cross-linking monomer, co polystyrene (function monomer) synthesizes Dy (III) IIP particle.After some authors [referring to Talanta, 60 (2003) 747-754] have also reported the γ-radiation of Dy IIP particle, for the improved Dy selectivity factor of La, Nd, Y and Lu.
The molecularly imprinted polymer particle of preparation is widely used in the separation of the medicine, amino acid derivativges, nucleotide base derivative of enantiomer, structurally associated etc.Therefore it is widely used in chemistry and pharmaceuticals industry, water quality purifying and garbage disposal.On the other hand, the preparation of ion imprinted polymer particle seldom is used for separating and gets in touch inorganic ions closely.Only at United States Patent (USP) the 6th, 251, No. 280; In 2001, people such as Dai have proposed this problem, but more general, and do not relate to from getting in touch closely and separate erbium the lanthanum.
Goal of the invention
The main purpose of this research is by prepare erbium IIP material with γ-radiation in the presence of the methyl methacrylate (MMA) (function monomer) of different content.
Another object of the present invention provides the method for preparing erbium IIP material by the photochemical polymerization as the time for exposure function.
Another object of the present invention provides the method for preparing erbium IIP material by the heat polymerization as EGDMA (cross-linking monomer) concentration function.
Another object of the present invention is to come from the lanthanum of other selections pre-concentration to isolate erbium with the IIP particle by solid phase extractions.
Summary of the invention
Therefore, the invention provides the synthetic method of the ion imprinted polymer particle that is used for solid phase extractions pre-concentration erbium ion, this method comprises:
(a) erbium ion and 5, and the 7-dichloro-8-hydroxyquinoline (5,7-dichloroquinoline-8-ol) form the mixed ligand ternary complex with 4-vinylpridine;
(b) this ternary complex is dissolved in the suitable pore former, forms the preceding mixture of polymerization.
(c) mixture in the step (b) is combined with function monomer and cross-linking monomer, and carry out polymerisation, obtain polymeric material by the method for γ-radiation or photochemical polymerization and thermal polymerization;
(d) polymeric material that obtains in the step (c) is ground, sieving, preparation erbium ion imprinted polymer particle;
(e) material that embeds with trace ion in the polymer particle of optionally lixiviate step of inorganic acid (d).
In one embodiment of this invention, described γ-radiation is to carry out as methyl methacrylate (function monomer) concentration function.
In another embodiment of the present invention, described photochemical polymerization is to carry out as UV radiated time function.
In another embodiment of the present invention, described thermal polymerization is to carry out as ethylene glycol dimethacrylate (cross-linking monomer) concentration function.
In another embodiment of the present invention, described function monomer is selected from 4-vinylpridine and methyl methacrylate.
In another embodiment of the present invention, described cross-linking monomer comprises ethylene glycol dimethacrylate.
In another embodiment of the present invention, with 2,2 '-azodiisobutyronitrile is realized described reaction as the initator of step (c).
In another embodiment of the present invention, after erbium ion imprinted polymer material drying, carry out grinding and sieving in the step (d).
In another embodiment of the present invention, be used for the inorganic acid of lixiviate and comprise HCl.
Brief description of drawings
In this specification institute accompanying drawing:
Fig. 1 represents 5,7-dichloro-8-hydroxyquinoline (DCQ), 4-vinylpridine (VP), DCQ+VP, Er
3++ DCQ+Er, Er
3++ VP and Er
3+The UV-visible absorption spectra of+DCQ+VP.
Fig. 2 is for forming the schematic diagram of ternary mixed ligand coordination compound.
Fig. 3 is the schematic diagram of polymer trace process.
Fig. 4 represents that methyl methacrylate (MMA) (function monomer) concentration is to using the Er by the synthetic IIP particle of γ-radiation
3+The effect of pre-concentration.
Fig. 5 represents that the UV-radiated time is to using the Er by the synthetic IIP particle of photochemical polymerization reaction
3+The effect of pre-concentration.
Fig. 6 represents that ethylene glycol dimethacrylate (EGDMA) (cross-linking monomer) concentration is to using the Er by the synthetic IIP particle of heat polymerization
3+The effect of pre-concentration.
Detailed description of the invention
The invention provides the synthetic method of selective erbium ion imprinted polymer particle, described grain Son has for the trace section of accessible and homology from the aqueous solution solid phase extractions of dilution The position.
Term used herein " ion imprinted polymer (IIP) " refers to by this way at seal The material of polymerization around the mark ion: when the trace ion is removed from described material, cavity or " seal The mark position " stay with the complementary material of this trace ion shape and size in. The IIP material is added Enter in the dilution that contains the trace ion, the trace position optionally with the trace ions binding. This combination so that above-mentioned adaptation material can be used for the trace ion from other similar ion Enrichment/separate. Notable feature of the present invention comprises the following aspects:
I) by thermal polymerization, photochemical polymerization and γ-synthetic IIP grain that adapts to of radiation polymerization reaction Son.
Ii) the preliminary treatment polymer is with this trace ion of lixiviate.
Iii) enrichment from the aqueous solution of dilution.
I) the synthetic erbium IIP material that adapts to
The synthetic erbium IIP material that adapts to comprises two key steps: (I) form with trace ion (erbium) The ternary mixed ligand coordination compound is with (II) the ternary mixed ligand coordination compound is poly-with MMA and EGDMA Close reaction. Being formed in the 2-methyl cellosolve (pore former) of ternary complex carried out. By note The forming process of record UV-visible spectrum monitoring complex. Fig. 1 represents 5,7-, two chloro-8-hydroxyl quinolines Quinoline (DCQ), 4-vinylpridine (VP), DCQ+VP, Er3++DCQ+Er、Er
3++ VP and Er3+The absorption spectrum of+DCQ+VP. These spectrum clearly illustrate that at 2-methyl cellosolve solution The formation (seeing Fig. 2) of middle ternary complex.
Ternary complex comes by the interpolation of function monomer (MMA) and cross-linking monomer (EGDMA) Trace. Only add 2 in thermal polymerization and photochemical polymerization, 2 '-azodiisobutyronitrile is anti-as polymerization The initator of answering. Resulting IIP material is dry in baking oven under 50 ℃, obtains erbium ion The IIP material. Fig. 3 is the schematic diagram of polymer trace process. These materials processes grind, sieving, Obtain erbium ion IIP particle. When Fig. 4, Fig. 5 and Fig. 6 show MMA concentration, UV-radiation Between and EGDMA concentration to using respectively by γ-radiation polymerization, photochemical polymerization and thermal polymerization The IIP that reaction is synthesized is to Er3+The effect of enrichment.
Ii) preliminary treatment IIP material is with lixiviate trace ion
Described trace ion, i.e. Er3+, by stirring 6 hours with 5N HCl solution, from polymerization Lixiviate is come out in the thing. Resulting IIP particle is dry in baking oven under 50 ℃, obtains erbium The IIP-SPE particle, it is used for from the aqueous solution of dilution enrichment erbium ion optionally.
Iii) enrichment Er from the aqueous solution of dilution3+
Studied in great detail with erbium IIP particle enrichment erbium ion from the aqueous solution of dilution. Fig. 4 table Show that the concentration of methyl methacrylate (MMA) is to using the Er of γ-radiation polymerization3+The erbium of IIP from The effect of sub-enrichment percentage. Fig. 5 represents that the UV-radiated time passes through photochemical polymerization to use The effect of the erbium enrichment percentage of the IIP particle that reaction is synthetic. Fig. 6 represents cross-linking monomer (EGDMA) concentration is in the process of using by the synthetic IIP particle enrichment erbium ion of heat polymerization In effect.
Therefore, the invention provides " the synthetic and method that is used for the adaptation IIP-SPE particle of extraction erbium ion ", the method comprises following correlation step:
(i) prepare the IIP particle by γ-radiation polymerization, photochemical polymerization and heat polymerization.
(ii) enrichment erbium ion from the aqueous solution of dilution.
(iii) erbium is separated from other lanthanide series.
Following examples have been described the synthetic of the ion imprinted polymer material that is used for selectivity solid phase extractions erbium ion.
Embodiment 1: γ-radiation polymerization
In the 50ml round-bottomed flask, add 1.0mM erbium chloride (0.44g), 3.0mMDCQ (0.64g) and 2mM VP (0.21g), and under agitation be dissolved in 5 or the 10ml 2-methyl cellosolve in.Add 4 (0.4g) or 8 (0.8g) and 12 (1.2g) mM MMA and 16 (3.17g) or 32 (6.34g) and 48 (9.52g) mM EGDMA, stir until obtaining homogeneous solution.Monomer mixture is transferred in the test tube, is cooled to 0 ℃, use N
2Purge 10 minutes and sealing.
Use Co
60The source, at 1M rad spoke γ-penetrate down with these solution irradiations 4 hours.Formed solid washes with water and is dry in baking oven under 50 ℃.Obtain having 4,8 and 5.70,9.43 and 14.27g polymeric material of 12mM function monomer respectively.The polymer that embeds erbium ion stirred 6 hours simultaneously with 50% (v/v) HCl lixiviate.In baking oven, obtain having 4,8 and 4.14,7.52 and 11.29g polymeric material of 12mM function monomer under 50 ℃ after the drying respectively.
Embodiment 2: the photochemical method polymerization
In the 50ml round-bottomed flask, add 1.0mM erbium chloride (0.44g), 3.0mMDCQ (0.64g) and 2.0mM VP (0.21g), and under agitation be dissolved in the 10ml 2-methyl cellosolve.Add 8mM MMA (0.8g), 32mM EGDMA (6.35g) and 50mg AIBN and stirring until obtaining homogeneous solution.Monomer mixture is transferred in the test tube, is cooled to 0 ℃, use N
2Purge 10 minutes and sealing.These solution came polymerization in 4,8 and 16 hours through UV radiation (300nm).Formed solid washes with water, and is dry in baking oven under 50 ℃.Obtain 7.55,9.85 and 9.95g polymeric material with UV radiation (300nm) 4,8 and 16h.The polymer that embeds erbium ion stirred 6 hours simultaneously with 50% (v/v) HCl lixiviate.In baking oven, distinguish 5.35,7.31 and the 7.36g polymeric material of handy UV radiation 4,8 and 16h under 50 ℃ after the drying.
Embodiment 3: thermal polymerization
In the 50ml round-bottomed flask, add 1.0mM erbium chloride (0.44g), 3.0mMDCQ (0.64g) and 2.0mM VP (0.21g), and under agitation be dissolved in the 10ml 2-methyl cellosolve.Add 8.0mM MMA (0.8g), 8,16 and 32mM EGDMA (1.59,3.17 and 6.34g) and 50mg AIBN, stirring is until obtaining homogeneous solution.Polyblend is cooled to 0 ℃, uses N
2Purge 10 minutes, sealing also adds thermal agitation 2 hours in about 80 ℃ oil bath.Formed solid washes with water, and is dry in baking oven under 50 ℃.Obtain having 4.32,5.50 and 8.84g polymeric material of 50%, 66% and 80% cross-linking monomer.The polymer that embeds erbium ion stirred 6 hours with 100ml 50% (v/v) HCl lixiviate, filter, under 50 ℃ in baking oven drying.Obtain 2.59,3.90 and 7.90g erbium ion imprinted polymer material.
Advantage of the present invention:
Liquid-liquid extracting method has replaced the conventional ion switching method, because the former speed reliably also Be easy to amplify. Yet, since Er with respect to the separation of Y near 1.0, so liquid-liquid is carried Access method needs the 40-50 counter-flow extraction in step. In addition, forcibly use a large amount of conducts molten The toxic chemical of agent and extractant. On the other hand, described in the invention based on adding seal The more environmental protection of the separation method of mark polymer particle, this relates to owing to use less chemicals And reduce cost and provide the Er for Y, Dy, Gd, Tb etc. better to select coefficient.
List of references:
Patent document
People such as WO9807671 Mark
Separating enatiomers by molecular imprinting (splitting enantiomer) with molecular engram
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Preparation and use of magnetically susceptible polymer particles (preparation of magnetosensitive polymer particle and application)
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Adsorbents for amino acids and peptide separation (amino acid separate use adsorbent) with peptide
US 5,461, people such as 175 Fischer
Method for separating enantiomers of aryloxipropanolaminederivatives and chiral solid phase chromatography material for use in themethod (the chiral solid phase chromatographic material that is used for separating the method for aryloxy propanol amine derivative enantiomer and is used for this method)
US 6,063, people such as 637 Arnold
Sensors for sugars and other metal binding analytes (sensor that is used for sugar and other metal bound analytes)
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Molecularly imprinted materials, method for their preparation anddevices employing such materials (device of molecular engram material, its preparation method and this material of application)
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Molecularly imprinted material made by template directed synthesis (by the molecular engram material of the synthetic preparation of template direction)
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Molecular receptors in metal oxide sol-gel materials (molecular receptor in metal oxide sol-gel rubber material)
US 6,255, people such as 461 Mosbach
Artificial antibodies to corticosteroids prepared by molecularimprinting is (by (the cortical hormone class man-made antibody) of molecular engram preparation
People such as US 2,003 049870 Magnus
Selective affinity material, preparation there of by molecularimprinting, and use of the same (selectivity affinitive material, prepare this material and application thereof) with molecular engram
US?2003?113234 Murray
Polymer based permeable membrane for removal of ions (being used for removing the polymer based on permeable membrane of deionization)
US?2003?059346 Murray
Method and apparatus for environmental phosphate/nitrate pollutionremoval using a selectively permeable molecularly imprinted polymermembrane (removing the method and apparatus of phosphate/nitrate pollutants in the environment with the selectively penetrating molecular imprinted polymer membrane)
US 6,248, people such as 842 Singh
Synthetic polymer matrices including pro-organised chelation sitesfor the selective and reversible binding of metals (the synthetic polymer substrate that contains the pre-organized chelating position that is useful on selectivity and reversible metal combination)
WO 99 15, people such as 707 John
Detection and extraction of an ion in a solution, particularly uraniumion (detection of the ion in the solution, particularly uranium ion and extraction)
US 6,251, people such as 280 Dai
Imprint coating synthesis of selective functionalized orderedmesoporous sorbents for separation and sensors (trace that is used to separate with the functional ordered mesopore adsorbent of Selectivity of Sensor applies synthetic)
Non-patent literature
People such as Garcia, Tetrahedron Lett., 39 (1998) 8651
Ionic imprinting effect in gadolinium/lanthanum separation (the ion blotting effect in gadolinium/lanthanum separation)
People such as Vigneau, Anal.Chim.Acta, 435 (2001) 75
Ionic imprinted resins based on EDTA and DTPA derivatives forlanthanides (III) separation (being used for the ion blotting resin that lanthanide series (III) separates) based on EDTA and DTPA derivative
People such as Vigneau, Chem.Lett. (2002) 202
Solid-Liquid separation of lanthanide/lanthanide andlanthanide/actinide using ionic imprinted polymer based on a DTPAderivative (utilization is based on the anion imprinted polymer solid-liquid SEPARATION OF La series elements/lanthanide series and the lanthanide series/acitinide of DTPA derivative)
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Claims (9)
1. be used for the synthetic method of the ion imprinted polymer particle of solid phase extractions pre-concentration erbium ion, described method comprises:
(a) with 5,7-dichloro-8-hydroxyquinoline and 4-vinylpridine form the mixed ligand ternary complex of erbium trace ion;
(b) described ternary complex is dissolved in the suitable pore former, forms the preceding mixture of polymerization;
(c) mixture in the step (b) is combined with function monomer and cross-linking monomer, and carry out polymerisation, obtain polymeric material by γ-radiation or photochemical polymerization and thermal polymerization;
(d) polymeric material that obtains in the step (c) is ground, sieving, preparation erbium ion imprinted polymer particle;
(e) with the material that embeds the trace ion in the polymer particle of optionally lixiviate step of inorganic acid (d).
2. the method for claim 1, wherein said γ-radiation are that the function as methyl methacrylate (function monomer) concentration carries out.
3. the method for claim 1, wherein said photochemical polymerization are that the function as the UV radiated time carries out.
4. the method for claim 1, wherein said thermal polymerization are that the function as ethylene glycol dimethacrylate (cross-linking monomer) concentration carries out.
5. the method for claim 1, wherein said function monomer is selected from 4-vinylpridine and methyl methacrylate.
6. the method for claim 1, wherein said cross-linking monomer comprises ethylene glycol dimethacrylate.
7. the method for claim 1, wherein said reaction is with 2,2 '-azodiisobutyronitrile is realized as the initator of step (c).
8. the method for claim 1, wherein grinding with sieving in the step (d) carried out after erbium ion imprinted polymer material drying.
9. the method for claim 1 wherein is used for the inorganic acid of lixiviate and comprises HCl.
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| CN101260170B (en) * | 2007-03-05 | 2011-08-17 | 成均馆大学校产学协力团 | Method for preparing surface-imprinted polymer microspheres in the form of core-shell for selective separation of heavy metal ions |
| CN103285837A (en) * | 2013-06-27 | 2013-09-11 | 武汉科梦环境工程有限公司 | Preparation method of adsorption material with high selectivity on different heavy metal ions |
| CN106979930A (en) * | 2017-05-23 | 2017-07-25 | 中国科学院地质与地球物理研究所 | A kind of method of free iron content in quantitative analysis Soil/Sediment Samples |
| CN115141305A (en) * | 2022-07-06 | 2022-10-04 | 中国科学院赣江创新研究院 | Functional polymer, preparation method thereof and method for preparing ion imprinted polymer by using functional polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100723919B1 (en) | 2006-02-16 | 2007-08-10 | 성균관대학교산학협력단 | Selective separation of heavy metal ion using the metal ion imprinted polymer(miip) |
| JP2010100708A (en) * | 2008-10-22 | 2010-05-06 | Mukogawa Gakuin | Molecularly imprinted polymer and method for preparing the same |
| KR101016231B1 (en) * | 2009-02-04 | 2011-02-25 | 성균관대학교산학협력단 | Method for preparing porous imprinted polymer particles for the selective separation of heavy metal ions |
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| GB2516215A (en) * | 2013-05-23 | 2015-01-21 | Univ Lincoln | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
| CN106552590A (en) * | 2016-11-21 | 2017-04-05 | 西北矿冶研究院 | Preparation method of heavy metal ion imprinted magnetic chitosan adsorbent |
| CN109364770B (en) * | 2018-11-28 | 2021-02-12 | 江苏大学 | Preparation method and application of gadolinium ion imprinting nano carbon material composite membrane |
| CN112791712B (en) * | 2021-01-05 | 2022-05-10 | 南开大学 | Adsorbent for removing protein-bound uremic toxin through blood perfusion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1436599A2 (en) * | 2001-10-16 | 2004-07-14 | The Johns Hopkins University | Molecularly imprinted polymer solution anion sensor |
| CN1226311C (en) * | 2002-06-26 | 2005-11-09 | 天津大学 | Magnetic composite microsphere of molecular blot polymer and its suspemsion polymerization process for preparing it |
-
2003
- 2003-12-31 AU AU2003296866A patent/AU2003296866A1/en not_active Abandoned
- 2003-12-31 CN CNB2003801109410A patent/CN100448526C/en not_active Expired - Fee Related
- 2003-12-31 WO PCT/IN2003/000427 patent/WO2005063382A1/en active Application Filing
- 2003-12-31 GB GB0610829A patent/GB2424893B/en not_active Expired - Fee Related
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101260170B (en) * | 2007-03-05 | 2011-08-17 | 成均馆大学校产学协力团 | Method for preparing surface-imprinted polymer microspheres in the form of core-shell for selective separation of heavy metal ions |
| CN103285837A (en) * | 2013-06-27 | 2013-09-11 | 武汉科梦环境工程有限公司 | Preparation method of adsorption material with high selectivity on different heavy metal ions |
| CN106979930A (en) * | 2017-05-23 | 2017-07-25 | 中国科学院地质与地球物理研究所 | A kind of method of free iron content in quantitative analysis Soil/Sediment Samples |
| CN106979930B (en) * | 2017-05-23 | 2018-04-24 | 中国科学院地质与地球物理研究所 | A kind of method of free iron content in quantitative analysis Soil/Sediment Samples |
| CN115141305A (en) * | 2022-07-06 | 2022-10-04 | 中国科学院赣江创新研究院 | Functional polymer, preparation method thereof and method for preparing ion imprinted polymer by using functional polymer |
| CN115141305B (en) * | 2022-07-06 | 2023-09-19 | 中国科学院赣江创新研究院 | Functional polymer, preparation method thereof and method for preparing ion imprinting polymer by using functional polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0610829D0 (en) | 2006-07-12 |
| GB2424893A (en) | 2006-10-11 |
| AU2003296866A1 (en) | 2005-07-21 |
| GB2424893B (en) | 2007-07-25 |
| WO2005063382A1 (en) | 2005-07-14 |
| JP2007518545A (en) | 2007-07-12 |
| JP4414396B2 (en) | 2010-02-10 |
| CN100448526C (en) | 2009-01-07 |
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