CN104788610A - Preparation method for micro hydrogel capable of detecting various heavy metal ions in water - Google Patents
Preparation method for micro hydrogel capable of detecting various heavy metal ions in water Download PDFInfo
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Abstract
The invention relates to the field of environmentally sensitive high polymer materials, in particular to a preparation method for a micro hydrogel capable of detecting various heavy metal ions in water. The preparation method for the micro hydrogel comprises the following steps: dissolving M1, M2, M3 and an initiator in water, performing the free radical copolymerization reaction under an oxygen free condition at 60-90 DEG C, adding an N,N-dimethyl formamide solution of M4 after 20 minutes of the copolymerization reaction, and continuously reacting for 6-24 hours; after the completion of the copolymerization reaction, dialyzing the obtained finished product for a week to obtain the purified ion micro hydrogel. Through the adoption of the micro hydrogel provided by the invention, various metal ions such as copper, nickel, zinc, cobalt, iron, lead, manganese, aluminum, chromium and barium of which the concentrations are at the grade of micron can be effectively identified visually; the preparation method and the reaction operation are simple, an emulsifier is not needed, the purification process is convenient, the process is simple and controllable, and the preparation method is suitable for industrialized production.
Description
Technical field
The invention relates to the polymeric material field of environment sensitive type, particularly a kind of preparation method that can detect micro-hydrogel of contents of many kinds of heavy metal ion.
Background technology
In recent years, sewage disposal becomes an important public health problem gradually, receives and pays close attention to widely.Heavy metal is topmost pollutent in water treatment procedure, and be usually present in industry and municipal wastewater, wherein industrial waste becomes the main source of natural water area heavy metal contamination.Heavy metal ion has mobility and toxicity because of it and is reported as priority control pollutent.When copper in body, zinc, cadmium, plumbous, mercury, iron, when the content of nickel and other metals exceedes tolerance level, can produce potential damaging influence to human body and other organism.
The patent of the preparation method of current detection of heavy metal ion material is existing a lot, but general raw material costly, or sensing range is narrower, is unfavorable for suitability for industrialized production and further scientific research.
Chinese patent CN102621113A discloses a kind of HAP nano-probe for detection of heavy metal ion in water and preparation method thereof, the surface adsorption effect utilizing HAP nano belt to assemble ball extremely strong makes heavy metal ion enrichment, and the organic active molecule that this nano-probe combines can produce photoluminescence phenomenon after meeting heavy metal ion, the detection of heavy metal ion can be realized by combined with fluorescent spectrum.The method sensing range is wide, and detection limit is low, but the preparation of desired raw material HAP nano belt assembling ball is comparatively loaded down with trivial details, affects its use range.
Chinese patent CN104140431A disclose a kind ofly to detect, the rhodamine fluorescence probe of separation of heavy metal ions and preparation method thereof, with rhodamine B (RhB) for raw material, make its end with azobenzene group by modification, prepare the rhodamine fluorescence probe that can detect mercury ion.Utilize the host-guest inclusion complex of nitrogen benzide and cyclodextrin, using the previously prepared cyclodextrin magnetic nano-particle obtained as sorbent material, make to be separated from solution under the effect of externally-applied magnetic field with the metal ion detected by the fluorescent probe of inclusion, utilize the photoreactivity of azobenzene group to realize repeatedly using of removing of heavy metal ion and cyclodextrin magnetic nano-particle.This invention need by distinguishing rhodamine fluorescence probe and the cyclodextrin magnetic nano-particle of synthesis modification compared with multi-step, process is comparatively loaded down with trivial details, and can only detect mercury ion, and practicality is not strong.
Chinese patent CN102914517A discloses a kind of sensor of the detected heavy metal ion be made up of superparamagnetism ferric oxide nano particle, Streptavidin, vitamin H and deoxynucleotide sequence.This invention preparation is comparatively simple, easy to operate, and this sensor can be recycled.But these invention desired raw material Streptavidin, vitamin H and deoxynucleotide etc. all costly, are not suitable for large-scale commercial production.
Up to the present, there are many reports about Heavy Metals in Waters ion detection both at home and abroad, but but substantially do not have about with the report of the micro-hydrogel of temperature sensitivity for carrier sense and enriching heavy metal ion.
Microgel is a kind of three-dimensional cross-linked polymeric colloid particle being of a size of micro/nano level, can uniform and stable dispersion and in solvent swelling state, have stronger expansion-contraction performance in good solvent.Wherein the research of stimulating responsive microgel especially receives the concern of people.When external environment changes, as temperature, pH value, solvent, salt concn, light, sound field, electric field, pressure etc., can there is expansion or the contraction change of volume in microgel, show corresponding responsiveness.Utilize this stimuli responsive characteristic, each fields such as drug controlled release, biosensor, chemical separation, catalyzer, switch can be applied in.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, provides One-step Synthesis can detect the method for micro-hydrogel of contents of many kinds of heavy metal ion.For solving the problems of the technologies described above, solution of the present invention is:
A kind of preparation method that can detect micro-hydrogel of contents of many kinds of heavy metal ion is provided, specifically comprise the steps: to get M1, M2, M3 and initiator is soluble in water, carry out free radicals copolymerization reaction under anaerobic, copolyreaction temperature is 60 ~ 90 DEG C, react the N adding M4 after 20 minutes, dinethylformamide solution, continues reaction 6 ~ 24 hours; After copolyreaction terminates, by products therefrom dialysis one week, i.e. the micro-hydrogel of ion of obtained purifying;
Wherein, the quality of initiator is 4 ~ 8% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, shared mass percent meets respectively separately:
Described initiator adopts 2,2 '-azo diisobutyl amidine dihydrochloride;
Described M1 is N-alkyl acryl amine monomer, and the chemical structural formula of N-alkyl acryl amine monomer is:
Wherein, R
1, R
2be respectively hydrogen atom, sec.-propyl, or R
1, R
2be respectively ethyl, ethyl;
Described M2 is the double bond compound containing tertiary amine group, and the chemical structural formula containing the double bond compound of tertiary amine group is:
Wherein, X is pyridines or imidazoles group;
Described M3 is alkyl polyhalides hydrocarbon compound, and the chemical structural formula of alkyl polyhalides hydrocarbon compound is:
Y-R
3-Y；
Wherein, R
3for carbonatoms is the straight chained alkyl of 2 ~ 6, Y is chlorine or bromine;
Described M4 is 4-(2-pyridylazo) Resorcinol, and the chemical structural formula of 4-(2-pyridylazo) Resorcinol is:
As further improvement, described M1, i.e. N-alkyl acryl amine monomer, adopt NIPA or the two ethyl acrylamide of N, N-.
As further improvement, described M2, namely containing the double bond compound of tertiary amine group, adopts 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine or N-vinyl imidazole.
As further improvement, described M3, i.e. alkyl polyhalides hydrocarbon compound, adopt 1,2-ethylene dichloride, glycol dibromide, 1,3-propylene dichloride, 1,3-dibromopropane, Isosorbide-5-Nitrae-dichlorobutane, Isosorbide-5-Nitrae-dibromobutane, 1,5-dichloropentane, 1, pentamethylene bromide, 1,6-dichloro hexane or 1,6-dibromo-hexane.
Principle of the present invention: M1 monomer resulting polymers is as responsive to envrionment temperature in poly N-isopropyl acrylamide etc., it has a low critical transition temperature (LCST) at about 31-32 DEG C, when temperature is lower than LCST, poly N-isopropyl acrylamide can be dissolved in deionized water completely, and when temperature is higher than LCST, poly N-isopropyl acrylamide water fast, due to the hydrogen bond in molecular chain and between molecular chain and hydrophobic interaction, is agglomerated into bead between poly N-isopropyl acrylamide molecular chain; Alkyl polyhalides hydrocarbon M3 as Isosorbide-5-Nitrae-dibromobutane etc. can with the tertiary amine group generation quaterisation of M2 as 4-vinylpridine and M4; If M1, M2, M3 and M4 are dissolved in deionized water, heat and add initiator initiation reaction, when solution temperature is greater than the LCST of M1 resulting polymers, namely stir under 60-90 DEG C of state of temperature, then there is free radicals copolymerization reaction on the one hand, there is quaterisation in the reunion bead of another aspect multipolymer simultaneously, the shape and size of multipolymer bead are fixed and bring the functional group that can detect heavy metal ion; Due to the reunion degree of multipolymer, the namely size of multipolymer bead and temperature correlation, can regulate the size of bead, obtaining the microgel bead of different size by controlling solution temperature; M4 contains the group such as amino, hydroxyl, can with heavy metal ion generation complexing color reaction, thus detect heavy metal ion; M1 monomer resulting polymers is responsive to envrionment temperature, and raised temperature can make complexing have micro-hydrogel aggregate and precipitate of heavy metal ion, realizes the enrichment of heavy metal ion.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention successfully introduces metal ion developer 4-(2-pyridylazo) Resorcinol being slightly soluble in water in micro-hydrogel structure unit, makes micro-hydrogel functionalization;
2, invention increases the solvability of 4-(2-pyridylazo) Resorcinol in water and stability, this micro-hydrogel at room temperature can be stablized and places half a year more than;
3, the present invention introduces Ionized quaternary ammonium salt while adopting quaterisation to make monomer occur to be cross-linked, and makes microgel obtain the good characteristic of poly ion liquid, extends the potential Application Areas of microgel;
4, by visual inspection, the micro-hydrogel of gained of the present invention effectively distinguishes that concentration is the many kinds of metal ions such as copper, nickel, zinc, cobalt, iron, lead, manganese, aluminium, chromium, barium of μM level;
5, the micro-hydrogel of gained of the present invention effectively detects the many kinds of metal ions such as copper, nickel, zinc, cobalt, iron, lead, manganese, aluminium, chromium, barium by ultraviolet visible spectrophotometry, and detectability reaches 10nM;
6, the micro-hydrogel of gained of the present invention has temperature sensitivity, after complexation heavy metal ion, produces aggregate and precipitate, thus realize the enrichment of heavy metal ion by raised temperature;
7, preparation method of the present invention, obtain micro-hydrogel particle diameter be 50-1000nm, and by changing the temperature and degree of crosslinking that aqueous solution constant temperature stirs in the preparation process of micro-hydrogel, obtain micro-hydrogel of different size;
8, preparation method of the present invention, operation simply, do not introduce emulsifying agent, and purge process is convenient, and technique is simply controlled, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo that can detect micro-hydrogel of contents of many kinds of heavy metal ion prepared by the present invention.
Fig. 2 is the graph of a relation (embodying the temperature sensitivity of micro-hydrogel) of the particle diameter that can detect micro-hydrogel of contents of many kinds of heavy metal ion prepared of the present invention and envrionment temperature.
Fig. 3 is particle diameter and colour-change schematic diagram after the different heavy metal ion of the micro-hydrogel complexing that can detect contents of many kinds of heavy metal ion prepared by the present invention.
Fig. 4 is that micro-hydrogel that can detect contents of many kinds of heavy metal ion prepared by the present invention adopts ultraviolet visible spectrophotometry to detect Cu
2+the uv-vis spectra schematic diagram of ion.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.
Embodiment 1
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.049g alkylene dihalide 1, 2-ethylene dibromide is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 60 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.043g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 6 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 7.14% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 65.71%, M2 be 8%, M3 be 14%, M4 is 12.29%.
Embodiment 2
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.049g alkylene dihalide 1, 6-dibromo-hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 70 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.043g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 6 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained, the transmission electron microscope photo of the micro-hydrogel of this copolyreaction gained and temperature sensitivity are as shown in Figure 1, 2.
In the present embodiment, the quality of initiator is 7.14% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 65.71%, M2 be 8%, M3 be 14%, M4 is 12.29%.
Embodiment 3
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.049g alkylene dihalide 1, 6-dibromo-hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 80 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.043g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 24 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 7.14% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 65.71%, M2 be 8%, M3 be 14%, M4 is 12.29%.
Embodiment 4
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.049g alkylene dihalide 1, 3-propylene dichloride is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 90 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.043g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 12 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 7.14% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 65.71%, M2 be 8%, M3 be 14%, M4 is 12.29%.
Embodiment 5
0.23g temperature sensitive monomer NIPA (NIPAm), 0.047g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.022g 1, 5-dichloropentane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 70 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.086g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 24 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 6.49% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 59.74%, M2 be 12.21%, M3 be 5.71%, M4 is 22.34%.
Embodiment 6
0.23g temperature sensitive monomer NIPA (NIPAm), 0.047g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.032g 1, 6-dichloro hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 70 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.065g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 6 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 6.68% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 61.5%, M2 be 12.57%, M3 be 8.56%, M4 is 17.38%.
Embodiment 7
0.23g temperature sensitive monomer NIPA (NIPAm), 0.047g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.044g 1, 4-dibromobutane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, under 70 DEG C of oil baths, isothermal reaction is after 20 minutes, add the N containing 0.043g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 12 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 6.87% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 63.19%, M2 be 12.91%, M3 be 12.09%, M4 is 11.81%.
Embodiment 8
0.23g temperature sensitive monomer NIPA (NIPAm), 0.019g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.010g 1, 2-ethylene dichloride is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.012g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction after 20 minutes under 70 DEG C of oil baths under nitrogen atmosphere condition, add the N containing 0.022g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 18 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 4.27% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 81.85%, M2 be 6.76%, M3 be 3.56%, M4 is 7.83%.
Embodiment 9
0.23g temperature sensitive monomer NIPA (NIPAm), 0.047g is containing tertiary amino groups monomer N-vinyl imidazoles (VIM) and 0.020g 1, 3-dibromopropane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction after 20 minutes under 70 DEG C of oil baths under nitrogen atmosphere condition, add the N containing 0.022g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 6 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 7.84% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 72.1%, M2 be 14.73%, M3 be 6.27%, M4 is 6.9%.
Embodiment 10
0.23g temperature sensitive monomer NIPA (NIPAm), 0.053g is containing tertiary amino groups monomer 4-vinylpridine and 0.013g 1, 4-dichlorobutane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction after 20 minutes under 70 DEG C of oil baths under nitrogen atmosphere condition, add the N containing 0.036g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 12 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 7.53% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 69.28%, M2 be 15.96%, M3 be 3.92%, M4 is 10.84%.
Embodiment 11
0.311g temperature sensitive monomer N, the two ethyl acrylamide of N-, 0.018g is containing tertiary amino groups monomer 3-vinyl pyridine and 0.009g 1, pentamethylene bromide is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.018g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction after 20 minutes under 70 DEG C of oil baths under nitrogen atmosphere condition, add the N containing 0.10g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 24 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 4.11% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 71.0%, M2 be 4.11%, M3 be 2.05%, M4 is 22.83%.
Embodiment 12
0.273g temperature sensitive monomer N, the two ethyl acrylamide of N-, 0.07g is containing tertiary amino groups monomer 2-vinyl pyridine and 0.074g 1, 6-dibromo-hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction after 20 minutes under 70 DEG C of oil baths under nitrogen atmosphere condition, add the N containing 0.022g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 6 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 5.69% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 62.19%, M2 be 15.95%, M3 be 16.87%, M4 is 5.01%.
Embodiment 13
0.34g temperature sensitive monomer N, the two ethyl acrylamide of N-, 0.10g is containing tertiary amino groups monomer 4-vinylpridine (4VP) and 0.09g alkylene dihalide 1, 6-dibromo-hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.034g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction after 20 minutes under 70 DEG C of oil baths under nitrogen atmosphere condition, add the N containing 0.15g 4-(2-pyridylazo) Resorcinol, dinethylformamide solution, continue reaction 12 hours, dialysis purification is after one week, namely micro-hydrogel that can detect contents of many kinds of heavy metal ion is obtained.
In the present embodiment, the quality of initiator is 5% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, separately shared mass percent meets respectively: M1 is 50%, M2 be 14.7%, M3 be 13.24%, M4 is 22.06%.
Embodiment 14
It is 1 × 10 that cupric nitrate, nickelous nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, lead nitrate, manganous nitrate, aluminum nitrate, chromium nitrate, nitrate of baryta are made into concentration
-3the aqueous solution of M; Micro-hydrogel that can detect contents of many kinds of heavy metal ion is made into the 0.125mg/mL aqueous solution, and is adjusted to different PH; Get the micro-hydrogel solution of 2mL, add the different heavy metal ion aqueous solution of 18 μ L respectively, mix after 5 minutes, detect.Such as, Fig. 3 to be pH value be 11 micro-hydrogel solution detectable level be particle diameter and the color of the different heavy metal ion of 9 μMs.
Embodiment 15
It is 1 × 10 that cupric nitrate, nickelous nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, lead nitrate, manganous nitrate, aluminum nitrate, chromium nitrate, nitrate of baryta are made into concentration
-3the aqueous solution of M; Micro-hydrogel that can detect contents of many kinds of heavy metal ion is made into 0.125mg/mL, and is adjusted to different PH; Get the micro-hydrogel solution of 2mL, add the 0-18 μ L heavy metal ion aqueous solution respectively, mix after 5 minutes, adopt ultraviolet spectrophotometry to detect.Such as, Fig. 4 to be pH value be 6 micro-hydrogel solution detectable level be the Cu of 1-9 μM
2+the UV spectrum of ion.
Embodiment 16
Cupric nitrate, nickelous nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, lead nitrate, manganous nitrate, aluminum nitrate, chromium nitrate, nitrate of baryta are made into the certain density aqueous solution; Micro-hydrogel that can detect contents of many kinds of heavy metal ion is made into the 2mg/mL aqueous solution, and is adjusted to different PH; Get the micro-hydrogel solution of 1mL, add the 0-10 μ L heavy metal ion aqueous solution respectively, mix after 5 minutes, detect.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, a lot of distortion can also be had.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. one kind can be detected the preparation method of micro-hydrogel of contents of many kinds of heavy metal ion, it is characterized in that, specifically comprise the steps: to get M1, M2, M3 and initiator is soluble in water, carry out free radicals copolymerization reaction under anaerobic, copolyreaction temperature is 60 ~ 90 DEG C, react the DMF solution adding M4 after 20 minutes, continue reaction 6 ~ 24 hours; After copolyreaction terminates, by products therefrom dialysis one week, i.e. the micro-hydrogel of ion of obtained purifying;
Wherein, the quality of initiator is 4 ~ 8% of M1, M2, M3, M4 tetra-kinds of reactant gross weights; And in M1, M2, M3, M4 tetra-kinds of reactants, shared mass percent meets respectively separately:
Described initiator adopts 2,2 '-azo diisobutyl amidine dihydrochloride;
Described M1 is N-alkyl acryl amine monomer, and the chemical structural formula of N-alkyl acryl amine monomer is:
Wherein, R
1, R
2be respectively hydrogen atom, sec.-propyl, or R
1, R
2be respectively ethyl, ethyl;
Described M2 is the double bond compound containing tertiary amine group, and the chemical structural formula containing the double bond compound of tertiary amine group is:
Wherein, X is pyridines or imidazoles group;
Described M3 is alkyl polyhalides hydrocarbon compound, and the chemical structural formula of alkyl polyhalides hydrocarbon compound is:
Y-R
3-Y；
Wherein, R
3for carbonatoms is the straight chained alkyl of 2 ~ 6, Y is chlorine or bromine;
Described M4 is 4-(2-pyridylazo) Resorcinol, and the chemical structural formula of 4-(2-pyridylazo) Resorcinol is:
2. a kind of preparation method that can detect micro-hydrogel of contents of many kinds of heavy metal ion according to claim 1, is characterized in that, described M1, i.e. N-alkyl acryl amine monomer, adopts NIPA or the two ethyl acrylamide of N, N-.
3. a kind of preparation method that can detect micro-hydrogel of contents of many kinds of heavy metal ion according to claim 1, it is characterized in that, described M2, namely containing the double bond compound of tertiary amine group, adopts 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine or N-vinyl imidazole.
4. a kind of preparation method that can detect micro-hydrogel of contents of many kinds of heavy metal ion according to claim 1, is characterized in that, described M3, i.e. alkyl polyhalides hydrocarbon compound, adopts 1,2-ethylene dichloride, 1,2-ethylene dibromide, 1,3-propylene dichloride, 1,3-dibromopropane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,5-dichloropentane, pentamethylene bromide, 1,6-dichloro hexane or 1,6-dibromo-hexane.
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| CN108478798A (en) * | 2018-02-06 | 2018-09-04 | 浙江大学 | A kind of preparation method for the micro- hydrogel that can load and be sustained simultaneously hydrophobe drug |
| CN108948266A (en) * | 2018-06-14 | 2018-12-07 | 浙江大学 | There is the preparation method of the highly selective active micro- hydrogel of detection to heavy metal lead |
| CN109078618A (en) * | 2018-07-19 | 2018-12-25 | 长安大学 | A kind of adsorbent material of Arsenic in tea ion, preparation method and applications |
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| CN108948266A (en) * | 2018-06-14 | 2018-12-07 | 浙江大学 | There is the preparation method of the highly selective active micro- hydrogel of detection to heavy metal lead |
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| CN113956397B (en) * | 2021-10-21 | 2022-06-17 | 四川大学 | Hg2+Selective response type high polymer material and preparation method thereof |
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