CN101033282A - Ion identification type intelligent macromolecule material, preparing method and use thereof - Google Patents
Ion identification type intelligent macromolecule material, preparing method and use thereof Download PDFInfo
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- CN101033282A CN101033282A CN 200710048725 CN200710048725A CN101033282A CN 101033282 A CN101033282 A CN 101033282A CN 200710048725 CN200710048725 CN 200710048725 CN 200710048725 A CN200710048725 A CN 200710048725A CN 101033282 A CN101033282 A CN 101033282A
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- isopropylacrylamide
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Abstract
The invention provides an ion identifying Intelligent Polymer- poly (N-isopropylacrylamide-copolymer-coumaron-15-crown-5-acrylamide), polymerized of N-isopropyl acrylamide monomer and benzo-15-crown-5- acrylyl monomer, and the structural formula is as the figture, in which, x is the molar percentage of benzo-15-crown-5-acrylamide group which range is 0.1% to 50%, 1-x is the molar percentage of N-isopropylacrylamide group which range is 50% to 99.9%. Its preparation process steps: ingredients, polymerization, purification and drying. The materials are used in production of sensors, actuators, fluorimetic analysis, and selective extraction of alkali metal ion.
Description
Technical field
The present invention relates to a kind of intelligent macromolecule material, a kind of organic high molecular polymer of specific ion and preparation method thereof in particularly a kind of optionally response environment.
Background technology
Intelligent macromolecule material (intelligent polymer) thus having physics in the response environment, chemistry and bioinformation changes physical properties or the function character jumpy that causes self.This character and the variation of occurring in nature organism response environment are made a response similar fast, thereby have caused domestic and international scientist's extensive concern and attention.Many metal ions are present in the organism widely, and organism is had vital role.Utilize intelligent macromolecule material to realize the identification and the response of metal ion especially alkalimetal ion are become hot research in recent years, demonstrate wide application prospect.
Based on the supramolecular complex of phendioxin 8-hat-6 is a kind ofly can optionally discern solution metal ionic intelligent macromolecule material, because the coordination of metal ion and 18-hat-6, the lower critical solution temperature LCST value that this material is undergone phase transition increases (sees Polymer 1993,34,4531).This kind material is fixed on the corresponding carrier can make the molecular recognition film, when temperature is higher than its LCST, discerns the solution metal ion by the crown ether group.Test shows that the intelligent macromolecule material with 18-hat-6 is to Ba
2+Very strong recognition capability (seeing Angew.Chem.Int.Ed, 2006,45,5630) is arranged.Because Ba
2+Importance in organism is not as alkalimetal ion, so the range of application of this intelligent macromolecule material in molecular recognition is restricted.
It is reported that the macromolecular material with poly-(phenylene vinylene support) structure of oxygen methyl 15-hat-5 para-orientation has the K in the response environment
+Ion causes the characteristic of quenching of fluorescence, thereby realizes K
+The recognition function of ion selectivity (seeing Angew.Chem.Int.Ed, 2000,39,3868); But this material is a kind of rigid macromolecule material of straight chain, can not change that it is water-soluble, the temperature variation in can not induced environment, and also fluorescent effect is not obvious.
Summary of the invention
The object of the present invention is to provide a kind of novel ion identification type intelligent macromolecule material and preparation method thereof, this kind material has temperature sensitive property, can change by discerning volume, close and distant water characteristic and the transmittance that specific alkalimetal ion causes polymer materials, can judge the kind and the concentration of alkalimetal ion again by the phase transformation of discerning specific alkalimetal ion initiation, and can change kind and the concentration of judging alkalimetal ion by the fluorescence intensity of discerning specific alkalimetal ion initiation, can also be used for the extracting and separating of Different Alkali metal ion.
Ion identification type intelligent macromolecule material called after of the present invention gathers (N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide), by N-N-isopropylacrylamide monomer (N-isopropylacrylamide, write a Chinese character in simplified form NIPAM) and phendioxin 5-hat-5-acrylamide monomer (Benzo-15crown-5-acrylamide, write a Chinese character in simplified form B15C5Am) be polymerized, structural formula is as follows:
In the said structure formula, x is 0.1%～50% for its scope of molecular fraction of phendioxin 5-hat-5-acrylamide group, and 1-x is that its scope of molecular fraction of N-N-isopropylacrylamide group is 50%～99.9%.
Poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention, its weight-average molecular weight is measured by gel chromatography, is 2000 to 20000; Its chemical structure is identified with the KBr tabletting method by infrared spectra, as shown in Figure 2, among Fig. 2, (a) be the infrared spectrogram of phendioxin 5-hat-5-acrylamide monomer, its characteristic peak is: 3269 (=CH), 1665 (C=O), 1632 (C=C), 1607 and 1514 (arom.), 1227 (=C-O), 1130 (C-O), 854 and 804 (arom.); (b) be the monomeric infrared spectrogram of N-N-isopropylacrylamide, its characteristic peak is: 2974 and 2934 (CH
3), 1649 (C=O), 1549 (C=C), 1388 and 1370 (CH
3); (c) be the infrared spectrogram of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide), its characteristic peak is: 2974 and 2934 (CH
3), 1649 (C=O), 1514 (arom.), 1227 (=C-O), 1130 (C-O), 854 and 804 (arom.).Can judge that by infrared spectrogram ion identification type intelligent macromolecule material of the present invention is polymerized by phendioxin 5-hat-5-acrylamide and N-N-isopropylacrylamide.
Poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) can form hydrogen bond with water molecules in the aqueous solution, have water-solublely, and its lower critical solution temperature (LCST) is (as shown in Figure 3) about 33 ℃; When having alkalimetal ion to exist in the environment, crown ether group complexing on alkalimetal ion and this intelligent macromolecule material main chain forms mixture (K especially
+Form 2: 1 mixture with it), make the hydrogen bond rupture that forms between crown ether functional group and the water molecules, change a kind of hydrophobic state into from a kind of hydrophily sharp, its structure becomes contraction schedule from solvent swelling state, (degree of reduction is relevant with the kind of alkalimetal ion and concentration, as shown in Figure 3, Figure 4 in its LCST reduction; Work as K
+When concentration was 0.075M, LCST reduced to 23 ℃, as shown in Figure 3).
The preparation method of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention, with phendioxin 5-hat-5-acrylamide monomer (Benzo-15crown-5-acrylamide, write a Chinese character in simplified form B15C5Am) and N-N-isopropylacrylamide monomer (N-isopropylacrylamide, write a Chinese character in simplified form NIPAM) be basic raw material, the molecular fraction of phendioxin 5-hat-5-acrylamide monomer is 0.1%～50%, the monomeric molecular fraction of N-N-isopropylacrylamide is 50%～99.9%, and processing step is as follows:
(1) batching
Under room temperature, normal pressure, phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer are dissolved in the solvent, be mixed with the monomer solution of volumetric molar concentration 1%～20%, and in monomer solution, add the polymerization starter Diisopropyl azodicarboxylate, the add-on of Diisopropyl azodicarboxylate be in the solution two kinds of monomer integral molar quantities 0.5%～5%;
(2) polyreaction
The monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation is heated to 50 ℃～100 ℃ reactions 4 hours～8 hours under oxygen free condition, promptly finishes polyreaction, its synthetic route as shown in Figure 1;
(3) separation and purification
After polyreaction is finished, be cooled to room temperature, under room temperature, normal pressure, precipitate with anhydrous diethyl ether, the add-on of anhydrous diethyl ether and sedimentation time produce white precipitate and precipitate no longer to increase with polymeric reaction solution exceeds, precipitation finishes after-filtration and gets solid matter, use the described dissolution with solvents of step (1) to filter the gained solid matter then, carry out aforementioned anhydrous diethyl ether precipitation and filtration again, precipitation-filtering number of times is at least twice;
(4) drying
Step (3) is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) after filtering gained solid matter drying for the last time.
In the aforesaid method, the used solvent of batching is tetrahydrofuran (THF) or N in the step (1), dinethylformamide; Oxygen free condition described in the step (2) is meant and will contains the monomer solution inflated with nitrogen deoxygenation of Diisopropyl azodicarboxylate and seal that (concrete operations are to feed nitrogen in the monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation, bubbling seals after removing dissolved oxygen in the solution at least in 30 minutes), perhaps will contain the monomer solution degassing deoxygenation of Diisopropyl azodicarboxylate and seal; In the aforesaid method, room temperature refers to indoor natural temperature, and normal pressure is meant 1 normal atmosphere.Various raw materials used in the aforesaid method all have the commercial goods.
As previously mentioned, crown ether group in poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention can form mixture with the alkalimetal ion complexing, cause that its LCST significantly descends, thereby can optionally discern the special alkalimetal ion in the solution.According to this characteristic, it can be had ion identification type transmitter and a stimulator as a kind of.
When the fluorescence spectrum that poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention is subjected to 325nm excites, demonstrate very strong excitation spectrum at the 327nm place, after forming mixture with special alkalimetal ion, consume part energy, thereby made fluorescence excitation spectrum show very strong quencher phenomenon (as shown in Figure 6).According to this character, it can be used in the ion identification type fluorometric analysis.
Crown ether group in poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention has very strong binding ability to special alkalimetal ion, according to this character, can be used for the selective extraction of alkalimetal ion is separated.
The present invention has following beneficial effect:
1, increases the kind of intelligent macromolecule material, widened the Application Areas of intelligent macromolecule material, helped the research and development of intelligent macromolecule material.
2, poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention have temperature sensitive property and ion identification characteristic, to alkalimetal ion, particularly K
+, have very strong identification responding ability, show the ion identification response function characteristic that existing intelligent macromolecule material did not have, remedied the deficiency that existing intelligent macromolecule material exists.
3, the preparation method is simple, and required equipment is a conventional equipment.
Description of drawings
Fig. 1 is the synthetic route chart of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention;
Fig. 2 is the infrared spectrogram of reactant and product, (a) is the infrared spectrogram of phendioxin 5-hat-5-acrylamide monomer among the figure, (b) being the monomeric infrared spectrogram of N-N-isopropylacrylamide, (c) is the infrared spectrogram of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention;
Fig. 3 is the phase transformation figure that the different types of alkalimetal ion of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention response causes;
Fig. 4 is that poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention response different concns alkalimetal ion causes the LCST variation diagram;
Fig. 5 is the K of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention
+Ion responsiveness transformation behavior synoptic diagram;
Fig. 6 is the fluorescent exciting spectrogram of the different types of alkalimetal ion of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention response;
Fig. 7 is the caused fluorescent quenching spirogram of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) the of the present invention different types of alkalimetal ion of response;
Fig. 8 is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of the present invention extraction results figure to the Different Alkali metal ion.
Embodiment
Present embodiment is a basic raw material with phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer, the molecular fraction of phendioxin 5-hat-5-acrylamide monomer is 0.1%, the monomeric molecular fraction of N-N-isopropylacrylamide is 99.9%, and processing step is as follows:
(1) batching
Under room temperature (15 ℃), normal pressure, phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer are dissolved in the tetrahydrofuran (THF), be mixed with the monomer solution of volumetric molar concentration 1%, and in monomer solution, add the polymerization starter Diisopropyl azodicarboxylate, the add-on of Diisopropyl azodicarboxylate be in the solution two kinds of monomer integral molar quantities 0.5%;
(2) polyreaction
Feed nitrogen in the monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation, bubbling was removed dissolved oxygen and the sealing in the solution in 30 minutes, placed 50 ℃ of water-baths then 8 hours, promptly finished polyreaction;
(3) separation and purification
After polyreaction is finished, be cooled to room temperature, under room temperature, normal pressure, precipitate with anhydrous diethyl ether, the add-on of anhydrous diethyl ether and sedimentation time produce white precipitate and precipitate no longer to increase with polymeric reaction solution exceeds, precipitation finishes after-filtration and gets solid matter, use tetrahydrofuran (THF) dissolution filter gained solid matter then, carry out aforementioned anhydrous diethyl ether precipitation and filtration again, precipitation-filtering number of times is three times;
(4) drying
Step (3) is filtered the gained solid matter for the third time and is placed in the baking oven in 50 ℃ of dryings 12 hours, is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) product.
Embodiment 2
Present embodiment is a basic raw material with phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer, the molecular fraction of phendioxin 5-hat-5-acrylamide monomer is 50%, the monomeric molecular fraction of N-N-isopropylacrylamide is 50%, and processing step is as follows:
(1) batching
Under room temperature (20 ℃), normal pressure, phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer are dissolved in N, in the dinethylformamide, be mixed with the monomer solution of volumetric molar concentration 20%, and in monomer solution, add the polymerization starter Diisopropyl azodicarboxylate, the add-on of Diisopropyl azodicarboxylate be in the solution two kinds of monomer integral molar quantities 5%;
(2) polyreaction
Feed nitrogen in the monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation, bubbling was removed dissolved oxygen and the sealing in the solution in 45 minutes, placed 100 ℃ of oil bath reactions 4 hours then, promptly finished polyreaction;
(3) separation and purification
After polyreaction is finished, be cooled to room temperature, under room temperature, normal pressure, precipitate with anhydrous diethyl ether, the add-on of anhydrous diethyl ether and sedimentation time produce white precipitate and precipitate no longer to increase with polymeric reaction solution exceeds, precipitation finishes after-filtration and gets solid matter, uses N then, dinethylformamide dissolution filter gained solid matter, carry out aforementioned anhydrous diethyl ether precipitation and filtration again, precipitation-filtering number of times is twice;
(4) drying
Step (3) is filtered the gained solid matter for the second time and was used infrared lamp dry 3 hours, is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) product.
Embodiment 3
Present embodiment is a basic raw material with phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer, the molecular fraction of phendioxin 5-hat-5-acrylamide monomer is 20%, the monomeric molecular fraction of N-N-isopropylacrylamide is 80%, and processing step is as follows:
(1) batching
Under room temperature (28 ℃), normal pressure, phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer are dissolved in the tetrahydrofuran (THF), be mixed with the monomer solution of volumetric molar concentration 3%, and in monomer solution, add the polymerization starter Diisopropyl azodicarboxylate, the add-on of Diisopropyl azodicarboxylate be in the solution two kinds of monomer integral molar quantities 2%;
(2) polyreaction
Feed nitrogen in the monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation, bubbling was removed dissolved oxygen and the sealing in the solution in 30 minutes, placed 80 ℃ of oil bath reactions 5 hours then, promptly finished polyreaction;
(3) separation and purification
After polyreaction is finished, be cooled to room temperature, under room temperature, normal pressure, precipitate with anhydrous diethyl ether, the add-on of anhydrous diethyl ether and sedimentation time produce white precipitate and precipitate no longer to increase with polymeric reaction solution exceeds, precipitation finishes after-filtration and gets solid matter, use tetrahydrofuran (THF) dissolution filter gained solid matter then, carry out aforementioned anhydrous diethyl ether precipitation and filtration again, precipitation-filtering number of times is three times;
(4) drying
Step (3) is filtered the gained solid matter for the third time and was used infrared lamp dry 3 hours, is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) product.
Embodiment 4
Present embodiment is a basic raw material with phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer, the molecular fraction of phendioxin 5-hat-5-acrylamide monomer is 10%, the monomeric molecular fraction of N-N-isopropylacrylamide is 90%, and processing step is as follows:
(1) batching
Under room temperature (30 ℃), normal pressure, phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer are dissolved in N, in the dinethylformamide, be mixed with the monomer solution of volumetric molar concentration 1%, and in monomer solution, add the polymerization starter Diisopropyl azodicarboxylate, the add-on of Diisopropyl azodicarboxylate be in the solution two kinds of monomer integral molar quantities 3%;
(2) polyreaction
Feed nitrogen in the monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation, bubbling was removed dissolved oxygen and the sealing in the solution in 40 minutes, placed 60 ℃ of water-bath reactions 6 hours then, promptly finished polyreaction;
(3) separation and purification
After polyreaction is finished, be cooled to room temperature, under room temperature, normal pressure, precipitate with anhydrous diethyl ether, the add-on of anhydrous diethyl ether and sedimentation time produce white precipitate and precipitate no longer to increase with polymeric reaction solution exceeds, precipitation finishes after-filtration and gets solid matter, uses N then, dinethylformamide dissolution filter gained solid matter, carry out aforementioned anhydrous diethyl ether precipitation and filtration again, precipitation-filtering number of times is three times;
(4) drying
Step (3) is filtered the gained solid matter for the third time and is placed in the baking oven in 50 ℃ of dryings 10 hours, is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) product.
Embodiment 5: the application of ion identification type transmitter and stimulator
It is 0.5% the aqueous solution that poly-(the N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of embodiment 4 preparation is mixed with massfraction, with ultraviolet spectrophotometer at 20 ℃～40 ℃ its transmittances of mensuration down; The above-mentioned massfraction of putting into equivalent then in four containers is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) aqueous solution of 0.5%, and adds the LiNO of 0.075M in four containers respectively
3, NaNO
3, KNO
3And CsNO
3, use ultraviolet spectrophotometer at 20 ℃～40 ℃ transmittances of measuring solution in each container down.That tests the results are shown in Figure 3.As can be seen from Figure 3: poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) in the aqueous solution that does not have alkalimetal ion to exist, its lower critical solution temperature (LCST) is about 33 ℃; In containing the aqueous solution of alkalimetal ion, its lower critical solution temperature (LCST) reduces, the degree that reduces is relevant with the kind of alkalimetal ion, and the variation of alkalimetal ion causes poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) LCST is big or small to be K
+＞Cs
+＞Na
+＞Li
+In addition, the variation of LCST size is also relevant with the alkalimetal ion concentration that adds in the solution, and total trend is that alkalimetal ion concentration is big more, and the variation of the LCST that causes is also big more, and alkalimetal ion concentration is K to the influence that LCST changes
+＞Cs
+＞Na
+＞Li
+, test result as shown in Figure 4.
The mechanism of lower critical solution temperature (LCST) variation that alkalimetal ion causes poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) is: when having alkalimetal ion to exist in the environment, the phendioxin 5-hat-5 and the alkalimetal ion complexing that contain in poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) form mixture, make phendioxin 5-be preced with the hydrogen bond rupture that forms between-5 functional groups and the water molecules, thereby be a kind of hydrophobic state from a kind of hydrophilic state-transition, demonstrate anti-phase phase transformation, lower critical solution temperature reduces.Because K
+Form stable 2: 1 sandwich shape mixtures (as shown in Figure 5) with phendioxin 5-hat-5 functional groups, thereby to make poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) be a kind of hydrophobic state from a kind of hydrophilic state-transition sharp, its lower critical solution temperature significantly reduces (seeing Fig. 3, Fig. 5), as can be seen from Figure 3, containing K
+In the ionic aqueous solution, poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) lower critical solution temperature (LCST) has been reduced to 23 ℃.
Because poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) has above-mentioned characteristic, thereby can optionally discern alkalimetal ion, especially K in the solution
+, can make poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) to become contraction schedule rapidly, so this kind material can be used in making ion identification type transmitter and stimulator by swelling state.
Embodiment 6: the application of ion identification type fluorometric analysis
's 7.4 Tris-HNO with poly-(the N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) of embodiment 4 preparation with pH
3Buffer preparation becomes concentration 6.67 * 10
-4The aqueous solution of M is to measure its fluorescence excitation spectrum under the condition of 325nm at 20 ℃, excitation wavelength with spectrophotofluorometer; In four containers, put into poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) aqueous solution of the above-mentioned concentration of equivalent then, and in four containers, add the LiNO of 50mM respectively
3, NaNO
3, KNO
3And CsNO
3, under 20 ℃, excitation wavelength are the condition of 325nm, measure the fluorescence excitation spectrum of solution in each container with spectrophotofluorometer.That tests the results are shown in Figure 6.As can be seen from Figure 6: the fluorescence spectrum that poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) is subjected to 325nm excites, and demonstrates very strong excitation spectrum at the 327nm place; When adding alkalimetal ion, the intensity of fluorescence excitation spectrum is reduced, the size of fluorescence excitation spectrum Strength Changes that alkalimetal ion causes poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) is K
+＞Cs
+＞Na
+＞Li
+
The mechanism of fluorescence excitation spectrum Strength Changes that alkalimetal ion causes poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) is: when having alkalimetal ion to exist in the environment, the phendioxin 5-hat-5 and the alkalimetal ion complexing that contain in poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) form mixture, changed poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) conformation in solution, consume part energy simultaneously, thereby made fluorescence excitation spectrum show intensity reduction phenomenon (claiming the quenching of fluorescence phenomenon again).Because K
+Form stable 2: 1 sandwich shape mixtures with phendioxin 5-hat-5 functional groups, the energy of consumption is more, thereby shows very strong quenching of fluorescence phenomenon.And, along with K
+Ionic concn is big more, and the fluorescent quenching amount is big more, test the results are shown in Figure 7.
Produce the quenching of fluorescence phenomenon because alkalimetal ion causes gathering (N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide),, can in the ion identification type fluorometric analysis, use used as ion identification type fluorometric analysis material according to this characteristic.
Embodiment 7: the isolating application of alkalimetal ion selective extraction
As mentioned above, when having alkalimetal ion to exist in the environment, the phendioxin 5-hat-5 and the alkalimetal ion complexing that contain in poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) form mixture, especially K
+Ion can form stable 2: 1 sandwich shape mixtures with phendioxin 5-hat-5 functional groups.According to this character, can carry out optionally extracting and separating to alkalimetal ion with it as the extracting and separating material.
Present embodiment is the dichloromethane solution of 3.9mM poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) with embodiment 4 prepared poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) compound concentrations, (picric acid is 0.148mM to get 10ml concentration respectively and be the dichloromethane solution of 3.9mM poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) and four kinds of picrate aqueous solution of equal volume, LiOH, NaOH, KOH, CsOH is respectively 10mM) mix respectively, fully after the extracting and separating, measure the picric concentration that extraction obtains in the dichloromethane solution respectively with ultraviolet spectrophotometer, test parameter is λ
m=374nm, ε=1.810
4LM
-1Cm
-1, extraction results such as Fig. 8, as can be seen from Figure 8, extraction quantity is K
+＞Cs
+＞Na
+＞Li
+
Poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) with embodiment 1, embodiment 2, embodiment 3 preparations carries out embodiment 5, embodiment 6, embodiment 7 described experiments, LCST, fluorescence excitation spectrum show intensity to be reduced and the alkalimetal ion extraction quantity, and all the variation tendency with embodiment 5, embodiment 6, embodiment 7 test results is identical.
Claims (8)
1, a kind of ion identification type intelligent macromolecule material---poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) is polymerized by N-N-isopropylacrylamide monomer and phendioxin 5-hat-5-acrylamide monomer, and structural formula is as follows:
In the said structure formula, x is the molecular fraction of phendioxin 5-hat-5-acrylamide group, and its scope is 0.1%～50%, and 1-x is the molecular fraction of N-N-isopropylacrylamide group, and its scope is 50%～99.9%.
2, the preparation method of claim 1 described poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide), it is characterized in that with phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer be basic raw material, the molecular fraction of phendioxin 5-hat-5-acrylamide monomer is 0.1%～50%, the monomeric molecular fraction of N-N-isopropylacrylamide is 50%～99.9%, and processing step is as follows:
(1) batching
Under room temperature, normal pressure, phendioxin 5-hat-5-acrylamide monomer and N-N-isopropylacrylamide monomer are dissolved in the solvent, be mixed with the monomer solution of volumetric molar concentration 1%～20%, and in monomer solution, add the polymerization starter Diisopropyl azodicarboxylate, the add-on of Diisopropyl azodicarboxylate be in the solution two kinds of monomer integral molar quantities 0.5%～5%;
(2) polyreaction
The monomer solution that contains Diisopropyl azodicarboxylate of step (1) preparation is heated to 50 ℃～100 ℃ reactions 4 hours～8 hours under oxygen free condition, promptly finishes polyreaction;
(3) separation and purification
After polyreaction is finished, be cooled to room temperature, under room temperature, normal pressure, precipitate with anhydrous diethyl ether, the add-on of anhydrous diethyl ether and sedimentation time produce white precipitate and precipitate no longer to increase with polymeric reaction solution exceeds, precipitation finishes after-filtration and gets solid matter, use the described dissolution with solvents of step (1) to filter the gained solid matter then, carry out aforementioned anhydrous diethyl ether precipitation and filtration procedure again, precipitation-filtering number of times is at least twice;
(4) drying
Step (3) is poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) after filtering gained solid matter drying for the last time.
3, the preparation method of poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) according to claim 2 is characterized in that the used solvent of batching is tetrahydrofuran (THF) or N in the step (1), dinethylformamide.
4,, it is characterized in that oxygen free condition described in the step (2) is meant the also sealing of monomer solution inflated with nitrogen deoxygenation that will contain Diisopropyl azodicarboxylate according to the preparation method of claim 2 or 3 described poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide).
5, the application of claim 1 described poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) in making transmitter.
6, the application of claim 1 described poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) in making stimulator.
7, described poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) application in fluorometric analysis of claim 1.
8, the application of claim 1 described poly-(N-N-isopropylacrylamide-copolymerization-phendioxin 5-hat-5-acrylamide) in the alkalimetal ion selective extraction is separated.
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| CNB2007100487258A CN100567350C (en) | 2007-03-26 | 2007-03-26 | Ion identification type intelligent macromolecule material and preparation method thereof and purposes |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628941B (en) * | 2013-11-15 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
| CN113956397A (en) * | 2021-10-21 | 2022-01-21 | 四川大学 | Hg2+Selective response type high polymer material and preparation method thereof |
| CN114573749A (en) * | 2022-03-10 | 2022-06-03 | 浙江大学杭州国际科创中心 | Room temperature phosphorescent copolymer and preparation method and application thereof |
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2007
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628941B (en) * | 2013-11-15 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
| CN113956397A (en) * | 2021-10-21 | 2022-01-21 | 四川大学 | Hg2+Selective response type high polymer material and preparation method thereof |
| CN113956397B (en) * | 2021-10-21 | 2022-06-17 | 四川大学 | Hg2+Selective response type high polymer material and preparation method thereof |
| CN114573749A (en) * | 2022-03-10 | 2022-06-03 | 浙江大学杭州国际科创中心 | Room temperature phosphorescent copolymer and preparation method and application thereof |
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| CN100567350C (en) | 2009-12-09 |
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