CN104788610B - 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 present invention is the polymeric material field with regard to environment sensitive type, more particularly to one kind can detect various heavy from
The preparation method of micro- hydrogel of son.
Background technology
In recent years, sewage disposal is increasingly becoming an important public health problem, of great interest.Heavy metal
It is topmost pollutant in water treatment procedure, in being typically found in industry and municipal wastewater, wherein industrial waste becomes natural
The main source of waters heavy metal pollution.Heavy metal ion is reported as priority control pollution because it has mobility and toxicity
Thing.When the content of internal copper, zinc, cadmium, lead, hydrargyrum, ferrum, nickel and other metals exceedes tolerance level, can be to human body and other lifes
Object produces potential damaging influence.
At present the patent of the preparation method of detection of heavy metal ion material is a lot, but general raw material is costly, or
Detection range is narrower, is unfavorable for industrialized production and further scientific research.
Chinese patent CN102621113A disclose a kind of HAP nano-probes for detection of heavy metal ion in water and its
Preparation method, assembling the extremely strong surface adsorption effect of ball using HAP nano belt makes heavy metal ion enrichment, and on the nano-probe
With reference to organic active molecule meet and can produce after heavy metal ion luminescence generated by light phenomenon, can combined with fluorescent spectrum realize to a huge sum of money
The detection of category ion.The method detection range is wide, and detection limit is low, but the preparation of needed raw material HAP nano belt assembling ball is more numerous
It is trivial, affect its use range.
Chinese patent CN104140431A discloses a kind of detectable, rhodamine fluorescence probe of separation of heavy metal ions
And preparation method thereof, with rhodamine B (RhB) as raw material, make its end with azobenzene group by modification, prepare
The rhodamine fluorescence probe of detectable mercury ion.Using diphenyl diimide and the host -guest inclusion complex of cyclodextrin, will be previously prepared
The cyclodextrin magnetic nano-particle for obtaining makes the fluorescent probe for being included with the metal ion for detecting additional as adsorbent
Separate from solution in the presence of magnetic field, using the photoreactivity of azobenzene group removing and the cyclodextrin of heavy metal ion are realized
Magnetic nano-particle is repeatedly used.The invention need to be by being respectively synthesized modified rhodamine fluorescence probe compared with multi-step
And cyclodextrin magnetic nano-particle, process is relatively complicated, and can only detect mercury ion, and practicality is not strong.
Chinese patent CN102914517A disclose one kind by superparamagnetism iron sesquioxide nano-particle, strepto- is affine
The sensor of the detectable heavy metal ion of element, biotin and deoxynucleotide sequence composition.The invention prepares relatively simple, behaviour
Facilitate, and the sensor can be recycled.However, invention needed raw material Streptavidin, biotin and the Deoxydization nucleotide
Deng costly, be not suitable for large-scale industrial production.
Up to the present, there are many reports with regard to Heavy Metals in Waters ion detection both at home and abroad, but with regard to temperature
The micro- hydrogel of sensitivity does not but have substantially for the report of carrier sense and enriching heavy metal ion.
Microgel is the three-dimensional cross-linked polymeric colloid particle that a kind of size is micro/nano level, can be uniform in good solvent
Stable dispersion and in solvent swelling state, with stronger expansion-contraction performance.The research of wherein stimulating responsive microgel is especially received
To the concern of people.When external environment changes, such as temperature, pH value, solvent, salinity, light, sound field, electric field, pressure are micro-
Gel can occur the expansion or shrinkage change of volume, show corresponding response.Using this stimuli responsive characteristic, can be by it
Apply field each in drug controlled release, biosensor, Chemical Decomposition, catalyst, switch etc..
The content of the invention
Present invention is primarily targeted at overcoming deficiency of the prior art, there is provided One-step Synthesis can detect various heavy
The method of micro- hydrogel of ion.To solve above-mentioned technical problem, the solution of the present invention is：
A kind of preparation method of the micro- hydrogel that can detect contents of many kinds of heavy metal ion is provided, following step is specifically included：Take
M1, M2, M3 and initiator are soluble in water, and free radicals copolymerization reaction is carried out under anaerobic, and copolyreaction temperature is 60～90
DEG C, the DMF solution of M4 is added after reacting 20 minutes, continue to react 6～24 hours；After copolyreaction terminates,
Products therefrom is dialysed one week, that is, the micro- hydrogel of ion of purification is obtained；
Wherein, the quality of initiator is the 4～8% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And M1, M2, M3,
In tetra- kinds of reactants of M4, each shared mass percent meets respectively：
The initiator adopts 2,2 '-azo diisobutyl amidine dihydrochloride；
The M1 is N- alkyl acryl amine monomers, and the chemical structural formula of N- alkyl acryl amine monomers is：
Wherein, R1、R2Respectively hydrogen atom, isopropyl, or R1、R2Respectively ethyl, ethyl；
The M2 is the double bond compound containing tertiary amine group, and the chemical structural formula of the double bond compound containing tertiary amine group is：
Wherein, X is pyridines or imidazoles group；
The M3 is alkyl polyhalides hydrocarbon compound, and the chemical structural formula of alkyl polyhalides hydrocarbon compound is：
Y-R3-Y；
Wherein, R3For the straight chained alkyl that carbon number is 2～6, Y is chlorine or bromine；
The M4 is 4- (2- pyridylazos) resorcinol, and the chemical structural formula of 4- (2- pyridylazos) resorcinol is：
As further improvement, the M1, i.e. N- alkyl acryls amine monomer, using NIPA or
The double ethyl acrylamides of N, N-.
As further improvement, the M2, the i.e. double bond compound containing tertiary amine group, using 2- vinylpyridines, 3-
Vinylpyridine, 4-vinylpridine or N- vinyl imidazoles.
Used as further improvement, the M3, i.e. alkyl polyhalides hydrocarbon compound adopt 1,2- dichloroethanes, 1,2- dibromos
Ethane, 1,3- dichloropropanes, 1,3- dibromopropanes, Isosorbide-5-Nitrae-dichloroetane, Isosorbide-5-Nitrae-dibromobutane, 1,5- dichloropentane, 1,5- bis-
Bromo pentane silane, 1,6- dichloro hexanes or 1,6- dibromo-hexane.
The principle of the present invention：M1 monomers resulting polymers such as poly-N-isopropyl acrylamide etc. is sensitive to ambient temperature, its
There is a low critical transition temperature (LCST) at 31-32 DEG C or so, when temperature is less than LCST, poly-N-isopropyl acrylamide can be complete
In deionized water, and when temperature is higher than LCST, poly-N-isopropyl acrylamide is insoluble in water, due to strand for CL
The hydrogen bond and hydrophobic interaction of interior and molecule interchain, poly-N-isopropyl acrylamide molecule interchain is agglomerated into bead；Polyhalo alkane
M3 such as Isosorbide-5-Nitrae-dibromobutanes etc. can occur quaterisation with the tertiary amine group of M2 such as 4-vinylpridine and M4；If by M1,
M2, M3 and M4 are dissolved in deionized water, heat and add initiator initiation reaction, when solution temperature is more than M1 resulting polymers
LCST, i.e., stir under 60-90 DEG C of state of temperature, then on the one hand free radicals copolymerization reaction, the group of another aspect copolymer occur
There is quaterisation in poly- bead simultaneously, make the shape and size of copolymer bead be fixed and take a detectable huge sum of money
The functional group of category ion；Due to the reunion degree of copolymer, that is, the size of copolymer bead it is related to temperature, by control
Solution temperature processed can adjust the size of bead, obtain various sizes of microgel bead；M4 contains the groups such as amino, hydroxyl,
Complexation chromogenic reaction can occur with heavy metal ion, so as to detect heavy metal ion；M1 monomer resulting polymers are to ambient temperature
Sensitivity, rising high-temperature can make complexation have micro- hydrogel aggregate and precipitate of heavy metal ion, realize the enrichment of heavy metal ion.
Compared with prior art, the invention has the beneficial effects as follows：
1st, the present invention successfully introduces metal ion developer 4- (the 2- pyrroles for being slightly soluble in water in micro- hydrogel structure unit
Pyridine azo) resorcinol, make micro- hydrogel functionalization；
2nd, the present invention improves dissolubility and stability of 4- (2- pyridylazos) resorcinol in water, micro- hydrogel
Stably can place more than half a year at room temperature；
3rd, the present invention makes monomer that the quaternary ammonium salt of ionizing is introduced while crosslinking using quaterisation, makes micro- solidifying
Glue obtains the good characteristic of poly ion liquid, extends the potential application field of microgel；
4th, the micro- hydrogel of present invention gained can observe by the naked eye effectively distinguish copper, nickel, zinc, cobalt, ferrum that concentration is μM level,
The many kinds of metal ions such as lead, manganese, aluminum, chromium, barium；
5th, the micro- hydrogel of present invention gained can by ultraviolet visible spectrophotometry effective detection copper, nickel, zinc, cobalt, ferrum,
The many kinds of metal ions such as lead, manganese, aluminum, chromium, barium, test limit reaches 10nM；
6th, the micro- hydrogel of present invention gained has temperature sensitivity, after complexation heavy metal ion, can be by rising high-temperature
Aggregate and precipitate is produced, so as to realize the enrichment of heavy metal ion；
7th, preparation method of the present invention, the particle diameter for obtaining micro- hydrogel is 50-1000nm, and can be by changing
Become the temperature and the degree of cross linking of the aqueous solution constant temperature stirring in the preparation process of micro- hydrogel obtaining various sizes of micro- water-setting
Glue；
8th, preparation method of the present invention, operation are simple, do not introduce emulsifying agent, and purge process is convenient, technique
It is simple controllable, it is adaptable to industrialized production.
Description of the drawings
Fig. 1 is the transmission electron microscope photo of the micro- hydrogel that can detect contents of many kinds of heavy metal ion prepared by the present invention.
Fig. 2 is the relation of the particle diameter with ambient temperature of the micro- hydrogel that can detect contents of many kinds of heavy metal ion prepared by the present invention
Figure (embodying the temperature sensitivity of micro- hydrogel).
Fig. 3 is grain after the micro- hydrogel complexation difference heavy metal ion that can detect contents of many kinds of heavy metal ion prepared by the present invention
Footpath and color change schematic diagram.
Fig. 4 be the present invention prepare can detect that micro- hydrogel of contents of many kinds of heavy metal ion adopts spectrophotometry
Method detects Cu2+The uv-vis spectra schematic diagram of ion.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is described in further detail with specific embodiment：
The professional and technical personnel that the following examples can make this professional is more fully understood the present invention, but not with any side
Formula limits the present invention.
Embodiment 1
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.028g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.049g alkylene dihalide glycol dibromides are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it
Fully dissolving, adds 0.025g initiators 2, and 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, in blanket of nitrogen foxing
Under part, under 60 DEG C of oil baths after isothermal reaction 20 minutes, the N, N- bis- of 4- containing 0.043g (2- pyridylazos) resorcinol are added
Methylformamide solution, continues to react 6 hours, after dialysis is purified one week, that is, obtains micro- water of detectable contents of many kinds of heavy metal ion
Gel.
In the present embodiment, the quality of initiator is the 7.14% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is that 8%, M3 is that M1 is 65.71%, M2
14%, M4 are 12.29%.
Embodiment 2
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.028g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.049g alkylene dihalides 1,6- dibromo-hexanes are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it
Fully dissolving, adds 0.025g initiators 2, and 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, in blanket of nitrogen foxing
Under part, under 70 DEG C of oil baths after isothermal reaction 20 minutes, the N, N- bis- of 4- containing 0.043g (2- pyridylazos) resorcinol are added
Methylformamide solution, continues to react 6 hours, after dialysis is purified one week, that is, obtains micro- water of detectable contents of many kinds of heavy metal ion
Gel；The transmission electron microscope photo and temperature sensitivity of the micro- hydrogel of copolyreaction gained is as shown in Figure 1, 2.
In the present embodiment, the quality of initiator is the 7.14% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is that 8%, M3 is that M1 is 65.71%, M2
14%, M4 are 12.29%.
Embodiment 3
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.028g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.049g alkylene dihalides 1,6- dibromo-hexanes are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it
Fully dissolving, adds 0.025g initiators 2, and 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, in blanket of nitrogen foxing
Under part, under 80 DEG C of oil baths after isothermal reaction 20 minutes, the N, N- bis- of 4- containing 0.043g (2- pyridylazos) resorcinol are added
Methylformamide solution, continues to react 24 hours, after dialysis is purified one week, that is, obtains micro- water of detectable contents of many kinds of heavy metal ion
Gel.
In the present embodiment, the quality of initiator is the 7.14% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is that 8%, M3 is that M1 is 65.71%, M2
14%, M4 are 12.29%.
Embodiment 4
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.028g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.049g alkylene dihalides 1,3- dichloropropanes are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it
Fully dissolving, adds 0.025g initiators 2, and 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, in blanket of nitrogen foxing
Under part, under 90 DEG C of oil baths after isothermal reaction 20 minutes, the N, N- bis- of 4- containing 0.043g (2- pyridylazos) resorcinol are added
Methylformamide solution, continues to react 12 hours, after dialysis is purified one week, that is, obtains micro- water of detectable contents of many kinds of heavy metal ion
Gel.
In the present embodiment, the quality of initiator is the 7.14% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is that 8%, M3 is that M1 is 65.71%, M2
14%, M4 are 12.29%.
Embodiment 5
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.047g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.022g 1,5- dichloropentane are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve,
0.025g initiators 2 are added, 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, under the conditions of nitrogen atmosphere, in 70
Under DEG C oil bath after isothermal reaction 20 minutes, the N of 4- containing 0.086g (2- pyridylazos) resorcinol, N- dimethyl formyls are added
Amine aqueous solution, continues to react 24 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 6.49% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 12.21%, M3 that M1 is 59.74%, M2
It is 22.34% for 5.71%, M4.
Embodiment 6
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.047g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.032g 1,6- dichloro hexane are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve,
0.025g initiators 2 are added, 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, under the conditions of nitrogen atmosphere, in 70
Under DEG C oil bath after isothermal reaction 20 minutes, the N of 4- containing 0.065g (2- pyridylazos) resorcinol, N- dimethyl formyls are added
Amine aqueous solution, continues to react 6 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 6.68% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 12.57%, M3 that M1 is 61.5%, M2
It is 17.38% for 8.56%, M4.
Embodiment 7
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.047g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.044g Isosorbide-5-Nitraes-dibromobutane are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve,
0.025g initiators 2 are added, 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, under the conditions of nitrogen atmosphere, in 70
Under DEG C oil bath after isothermal reaction 20 minutes, the N of 4- containing 0.043g (2- pyridylazos) resorcinol, N- dimethyl formyls are added
Amine aqueous solution, continues to react 12 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 6.87% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 12.91%, M3 that M1 is 63.19%, M2
It is 11.81% for 12.09%, M4.
Embodiment 8
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.019g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.010g 1,2- dichloroethanes are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve,
0.012g initiators 2 are added, 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, in 70 DEG C under the conditions of nitrogen atmosphere
Under oil bath after isothermal reaction 20 minutes, the DMF of 4- containing 0.022g (2- pyridylazos) resorcinol is added
Solution, continues to react 18 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 4.27% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 6.76%, M3 that M1 is 81.85%, M2
It is 7.83% for 3.56%, M4.
Embodiment 9
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.047g monomer N-vinyls containing tertiary amino groups miaow
Azoles (VIM) and 0.020g 1,3- dibromopropane are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve,
0.025g initiators 2 are added, 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, in 70 DEG C under the conditions of nitrogen atmosphere
Under oil bath after isothermal reaction 20 minutes, the DMF of 4- containing 0.022g (2- pyridylazos) resorcinol is added
Solution, continues to react 6 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 7.84% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 14.73%, M3 that M1 is 72.1%, M2
It is 6.9% for 6.27%, M4.
Embodiment 10
0.23g temperature sensitive monomer NIPAs (NIPAm), 0.053g monomers containing tertiary amino groups 4- vinylpyridines
Pyridine and 0.013g Isosorbide-5-Nitraes-dichloroetane are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve, and adds
0.025g initiators 2,2 '-azo diisobutyl amidine dihydrochloride, are sufficiently stirred for, under the conditions of nitrogen atmosphere under 70 DEG C of oil baths
After isothermal reaction 20 minutes, the DMF solution of 4- containing 0.036g (2- pyridylazos) resorcinol is added, after
Continuous reaction 12 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 7.53% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 15.96%, M3 that M1 is 69.28%, M2
It is 10.84% for 3.92%, M4.
Embodiment 11
0.311g temperature sensitive monomers N, the double ethyl acrylamides of N-, 0.018g monomers containing tertiary amino groups 3- vinylpyridines and
0.009g pentamethylene bromides are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve, and adds
0.018g initiators 2,2 '-azo diisobutyl amidine dihydrochloride, are sufficiently stirred for, under the conditions of nitrogen atmosphere under 70 DEG C of oil baths
After isothermal reaction 20 minutes, the DMF solution of 4- containing 0.10g (2- pyridylazos) resorcinol is added, after
Continuous reaction 24 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 4.11% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is that 4.11%, M3 is that M1 is 71.0%, M2
2.05%, M4 are 22.83%.
Embodiment 12
0.273g temperature sensitive monomers N, the double ethyl acrylamides of N-, 0.07g monomers containing tertiary amino groups 2- vinylpyridines and
0.074g 1,6- dibromo-hexane is dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes it fully dissolve, and adds
0.025g initiators 2,2 '-azo diisobutyl amidine dihydrochloride, are sufficiently stirred for, under the conditions of nitrogen atmosphere under 70 DEG C of oil baths
After isothermal reaction 20 minutes, the DMF solution of 4- containing 0.022g (2- pyridylazos) resorcinol is added, after
Continuous reaction 6 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 5.69% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And
In tetra- kinds of reactants of M1, M2, M3, M4, each shared mass percent meets respectively：It is 15.95%, M3 that M1 is 62.19%, M2
It is 5.01% for 16.87%, M4.
Embodiment 13
0.34g temperature sensitive monomers N, N- double ethyl acrylamide, 0.10g monomers containing tertiary amino groups 4-vinylpridines
(4VP) with 0.09g alkylene dihalides 1,6- dibromo-hexanes are dissolved in deionized water, and the stirring under the conditions of nitrogen atmosphere makes its abundant
Dissolving, adds 0.034g initiators 2, and 2 '-azo diisobutyl amidine dihydrochloride is sufficiently stirred for, under the conditions of nitrogen atmosphere
Under 70 DEG C of oil baths after isothermal reaction 20 minutes, the N of 4- containing 0.15g (2- pyridylazos) resorcinol, N- dimethyl methyls are added
Amide solution, continues to react 12 hours, after dialysis is purified one week, that is, obtains micro- hydrogel of detectable contents of many kinds of heavy metal ion.
In the present embodiment, the quality of initiator is the 5% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And M1,
In tetra- kinds of reactants of M2, M3, M4, each shared mass percent meets respectively：It is that 14.7%, M3 is that M1 is 50%, M2
13.24%, M4 are 22.06%.
Embodiment 14
By copper nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, ferric nitrate, plumbi nitrass, manganese nitrate, aluminum nitrate, chromic nitrate, nitric acid
Barium is made into concentration for 1 × 10-3The aqueous solution of M；Micro- hydrogel of detectable contents of many kinds of heavy metal ion is made into into 0.125mg/mL water
Solution, and adjust to different PH；The micro- hydrogel solutions of 2mL are taken, 18 μ L difference heavy metal ion aqueous solutions, mixing is separately added into
After 5 minutes, detected.For example, Fig. 3 for different heavy metals that micro- hydrogel solution detectable concentration that pH value is 11 is 9 μM from
The particle diameter and color of son.
Embodiment 15
By copper nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, ferric nitrate, plumbi nitrass, manganese nitrate, aluminum nitrate, chromic nitrate, nitric acid
Barium is made into concentration for 1 × 10-3The aqueous solution of M；Micro- hydrogel of detectable contents of many kinds of heavy metal ion is made into into 0.125mg/mL, and
Adjust to different PH；The micro- hydrogel solutions of 2mL are taken, 0-18 μ L heavy metal ion aqueous solutions are separately added into, after mixing 5 minutes,
Detected using ultraviolet spectrophotometry.For example, Fig. 4 is 1-9 μM for micro- hydrogel solution detectable concentration that pH value is 6
Cu2+The ultraviolet spectra of ion.
Embodiment 16
By copper nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, ferric nitrate, plumbi nitrass, manganese nitrate, aluminum nitrate, chromic nitrate, nitric acid
Barium is made into certain density aqueous solution；Micro- hydrogel of detectable contents of many kinds of heavy metal ion is made into into 2mg/mL aqueous solutions, and is adjusted
Save to different PH；The micro- hydrogel solutions of 1mL are taken, 0-10 μ L heavy metal ion aqueous solutions are separately added into, after mixing 5 minutes, is entered
Row detection.
Finally it should be noted that listed above is only specific embodiment of the invention.It is clear that the invention is not restricted to
Above example, can also there is many variations.One of ordinary skill in the art can directly lead from present disclosure
The all deformations for going out or associating, are considered as protection scope of the present invention.
Claims (4)
1. a kind of preparation method of the micro- hydrogel that can detect contents of many kinds of heavy metal ion, it is characterised in that specifically include following steps
Suddenly：Take M1, M2, M3 and initiator is soluble in water, free radicals copolymerization reaction is carried out under anaerobic, copolyreaction temperature is 60
～90 DEG C, the DMF solution of M4 is added after reacting 20 minutes, continue to react 6～24 hours；Copolyreaction is tied
Shu Hou, products therefrom is dialysed one week, that is, the micro- hydrogel of ion of purification is obtained；
Wherein, the quality of initiator is the 4～8% of tetra- kinds of reactant gross weights of M1, M2, M3, M4；And in M1, M2, M3, M4 tetra-
In planting reactant, each shared mass percent meets respectively：
The initiator adopts 2,2 '-azo diisobutyl amidine dihydrochloride；
The M1 is N- alkyl acryl amine monomers, and the chemical structural formula of N- alkyl acryl amine monomers is：
Wherein, R1、R2Respectively hydrogen atom, isopropyl, or R1、R2Respectively ethyl, ethyl；
The M2 is the double bond compound containing tertiary amine group, and the chemical structural formula of the double bond compound containing tertiary amine group is：
Wherein, X is pyridines or imidazoles group；
The M3 is alkyl polyhalides hydrocarbon compound, and the chemical structural formula of alkyl polyhalides hydrocarbon compound is：
Y-R3-Y；
Wherein, R3For the straight chained alkyl that carbon number is 2～6, Y is chlorine or bromine；
The M4 is 4- (2- pyridylazos) resorcinol, and the chemical structural formula of 4- (2- pyridylazos) resorcinol is：
2. the preparation method of a kind of micro- hydrogel that can detect contents of many kinds of heavy metal ion according to claim 1, its feature
It is, the M1, i.e. N- alkyl acryls amine monomer, using NIPA or the double ethyl acrylamides of N, N-.
3. the preparation method of a kind of micro- hydrogel that can detect contents of many kinds of heavy metal ion according to claim 1, its feature
It is, the M2, i.e. the double bond compound containing tertiary amine group, using 2- vinylpyridines, 3- vinylpyridines, 4- vinylpyridines
Pyridine or N- vinyl imidazoles.
4. the preparation method of a kind of micro- hydrogel that can detect contents of many kinds of heavy metal ion according to claim 1, its feature
Be, the M3, i.e. alkyl polyhalides hydrocarbon compound adopt 1,2- dichloroethanes, glycol dibromide, 1,3- dichloropropanes, 1,
3- dibromopropanes, Isosorbide-5-Nitrae-dichloroetane, Isosorbide-5-Nitrae-dibromobutane, 1,5- dichloropentane, pentamethylene bromide, 1,6- dichloro hexanes or
1,6- dibromo-hexane.
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