CN109337038B - 2, 5-dihydroxy terephthalic acid polyurethane and preparation method and application thereof - Google Patents
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention provides 2, 5-dihydroxy terephthalic acid polyurethane and a preparation method or application thereof, belonging to the technical field of polyurethane preparation. The 2, 5-dihydroxy terephthalic acid polyurethane has a structure shown in a formula 1. The invention also provides a preparation method of the 2, 5-dihydroxy terephthalic acid polyurethane, which is obtained by adding hexamethyl diisocyanate and 2, 5-dihydroxy terephthalic acid into a reaction vessel, then adding an end-capping reagent, a catalyst and an organic solvent, and reacting under anhydrous and anaerobic conditions. The invention also provides application of the 2, 5-dihydroxy terephthalic acid polyurethane as a fluorescence quenching sensor in detecting explosive 2,4, 6-trinitrophenol. The sensor has good selectivity and sensitivity to 2,4, 6-trinitrophenol (can efficiently detect TNP, has good response to low-concentration TNP, and has a detection limit as low as 10)‑10M。
Description
Technical Field
The invention belongs to the technical field of polyurethane preparation, and particularly relates to 2, 5-dihydroxy terephthalic acid polyurethane and a preparation method or application thereof.
Background
In the 21 st century, more and more bombs have been attacking events that seriously threaten the safety of human society. The rapid and highly selective detection of explosives has become a hot problem in today's society. The explosive power of TNP is especially strong compared to many nitroaromatics. And TNP is also an environmental pollutant of farmland and underground water, and indirectly harms human health. Therefore, it is highly desirable to find a method for detecting TNP rapidly and with high selectivity. Compared with explosion detection technologies such as gas chromatography, mass spectrometry, surface enhanced Raman spectroscopy, electrochemical methods and the like, the fluorescence detection method has the advantages of high sensitivity, simplicity, convenience, quick response time, low cost and the like.
Polyurethanes are the most widely used class of non-conjugated polymers, and have found wide applications in the fields of shape memory, adjustable performance, building insulation, furniture and bedding, etc. A large number of heteroatoms (O, N) are present in the non-conjugated polyurethane chain, so that the polyurethane acts as an electron donor and the nitroaromatic compound acts as an electron acceptor, and a Photoexcited Electron Transfer (PET) process may occur between the polyurethane and the aromatic compound.
Disclosure of Invention
The invention provides 2, 5-dihydroxy terephthalic acid polyurethane and a preparation method or application thereof, and the polyurethane derivative can be used for quickly detecting a fluorescence quenching sensor of explosive 2,4, 6-Trinitrophenol (TNP).
The invention firstly provides a 2, 5-dihydroxyterephthalic acid polyurethane, M thereofn＝600～900g mol-1The structure is shown as formula 1:
in the formula 1, m represents the repeating number of main repeating units on an oligomer chain, and m is 2.6-4; n represents the repeated number of the polyethylene glycol monomethyl ether part as the end capping agent, and n is 1.3-4.8.
The invention also provides a preparation method of the 2, 5-dihydroxy terephthalic acid polyurethane, which comprises the following steps:
under the protection of nitrogen, adding hexamethyl diisocyanate and 2, 5-dihydroxy terephthalic acid into a reaction vessel, then adding a blocking agent, a catalyst and an organic solvent, reacting under anhydrous and anaerobic conditions, cooling to room temperature after the reaction is finished, and precipitating to obtain the 2, 5-dihydroxy terephthalic acid polyurethane.
Preferably, the molar ratio of the 2, 5-dihydroxyterephthalic acid to the hexamethyldiisocyanate is 1 (1.2-1.6).
Preferably, the end-capping agent is polyethylene glycol monomethyl ether, and the catalyst is triethylene diamine.
Preferably, the solvent is tetrahydrofuran.
Preferably, the reaction temperature is 65-75 ℃, and the reaction time is 5-8 h.
Preferably, the molar ratio of the end-capping agent to the 2, 5-dihydroxyterephthalic acid is 1: (0.56-1.32).
The invention also provides application of the 2, 5-dihydroxy terephthalic acid polyurethane as a fluorescence quenching sensor in detecting explosive 2,4, 6-Trinitrophenol (TNP).
The invention has the advantages of
The invention provides 2, 5-dihydroxy terephthalic acid polyurethane and a preparation method or application thereof, the polyurethane derivative is prepared by one-pot reaction, and the derivative is successfully used for preparing a fluorescence quenching sensor for detecting explosive (TNP), the sensor has good selectivity and sensitivity on 2,4, 6-Trinitrophenol (TNP), can efficiently detect the TNP, has good response on low-concentration TNP, and has the detection limit as low as 10-10And M. The invention has the advantages of simple synthesis method, low cost, convenient operation, high detection sensitivity, rapid response and high fluorescence intensity, can realize naked eye detection and has wide application prospect.
Drawings
FIG. 1 shows the preparation of 2, 5-dihydroxyterephthalic acid polyurethane obtained in example 1 of the present invention1H-NMR spectrum;
FIG. 2 is a graph showing an infrared absorption spectrum of polyurethane 2, 5-dihydroxyterephthalic acid obtained in example 1 of the present invention;
FIG. 3 is a graph showing the change in fluorescence of the 2, 5-dihydroxyterephthalic acid polyurethane solution obtained in example 1 according to the present invention with increasing TNP addition;
FIG. 4 is a bar graph showing the selectivity of polyurethane 2, 5-dihydroxyterephthalic acid to various nitroaromatics obtained in example 1 of the present invention;
FIG. 5 shows UV absorption/fluorescence emission spectra of 2, 5-dihydroxy terephthalic acid polyurethane obtained in example 1 of the present invention and UV absorption spectra of various nitroaromatics;
FIG. 6 is a graph comparing the HOMO/LUMO energy levels of 2, 5-dihydroxyterephthalic acid polyurethane obtained in example 1 of the present invention with various nitroaromatics;
FIG. 7 is a graph showing the effect of the 2, 5-dihydroxy terephthalic acid polyurethane test paper obtained in example 1 on TNP under ultraviolet irradiation.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention
Example 1
Hexamethyldiisocyanate (3.14mmol) and 2, 5-dihydroxyterephthalic acid (2.62mmol) were added to a 25mL round-bottomed flask, and then the blocking agents polyethylene glycol monomethyl ether (M) were added to the flaskW200) (1.98mmol) and 10mL of catalyst DABCO (12mg) tetrahydrofuran, under the protection of nitrogen and under the anhydrous and oxygen-free conditions, slowly heating to 75 ℃, stirring and refluxing for 7h, cooling to room temperature after the reaction is finished, and precipitating from excessive diethyl ether to obtain a white viscous product, namely the 2, 5-dihydroxy terephthalic acid polyurethane. The reaction process is as follows:
the 2, 5-dihydroxyterephthalic acid polyurethane described in example 1 was subjected to1H-NMR and infrared absorption Spectroscopy analysis, and from the analysis results and the types of the reaction raw materials, Mn 716g mol of the polyurethane having the structure shown in formula (1) was calculated-1.
FIG. 1 shows the preparation of 2, 5-dihydroxyterephthalic acid polyurethane obtained in example 1 of the present invention1H-NMR(500MHz,DMSO-d6) The spectrogram can clearly see that methylene hydrogen nuclei exist in PEG at the position of 3.36-3.69 ppm; hydrogen nuclei on methylene of hexamethylene diisocyanate exist at 1.29-1.45 ppm and 2.63-2.98 ppm; at 12.41ppm, the hydroxyl nucleus of 2, 5-dihydroxyterephthalic acid was present.
2. Infrared absorption spectrum analysis:
FIG. 2 is an infrared absorption spectrum of 2, 5-dihydroxyterephthalic acid polyurethane obtained in example 1 of the present invention, from which it can be seen from FIG. 2 that 3323cm-1Is the absorption peak of the stretching vibration of N-H in carbamate; 2859 and 2941cm-1Is the stretching vibration peak of methyl and methylene; 1704cm-1The position is a stretching vibration peak of C ═ O; 1193cm-1The peak is the stretching vibration peak of C-O-C in the urethane group.
FIG. 3 is a graph showing the fluorescence emission spectrum of 2, 5-dihydroxyterephthalic acid Polyurethane (PU) obtained in example 1 of the present invention, the PU has better solubility in acetonitrile-water mixed solvent (1:1v/v) and strong green emission, and the photoluminescence quantum efficiency is 82%, as shown in FIG. 3a, PU (10. mu.M) has a strong emission peak at 527nm, the fluorescence intensity gradually decreases with the increase of the amount of TNP added, and 91% of the fluorescence is quenched when TNP is added to 30. mu.M, as shown in FIG. 3b, the Stern-Volmer curve is in a linear relationship at lower concentration, and the quenching constant is 1.22 × 105m-1And shows a super-large quenching effect at a high concentration. Limit of detection (LOD) of 10-10M，～0.229ag/cm2The sensitivity to TNP response is high.
FIG. 4 is a bar graph showing the selectivity of polyurethane 2, 5-dihydroxyterephthalic acid to various nitroaromatics obtained in example 1 of the present invention; as can be seen from FIG. 4, under the same conditions, other nitroaromatics (e.g., p-nitrobenzene, 3-nitrotoluene: mNT, 2, 4-dinitrotoluene: 2,4-DNT, p-nitrotoluene: NT, p-nitrobenzene: DNB, 2,4, 6-trinitrotoluene: TNT, etc.) have little effect on quenching PU fluorescence. The presence of these nitroaromatics hardly influences the quenching response of PU to TNP. These results clearly show that PU is very selective for TNP and very interference resistant for other classes of nitroaromatics.
FIG. 5 shows UV absorption/fluorescence emission spectra of 2, 5-dihydroxy terephthalic acid polyurethane obtained in example 1 of the present invention and UV absorption spectra of various nitroaromatics; as shown in FIG. 5a, there was observed an overlap between the absorption spectrum of TNP and the emission spectrum of PU, but little overlap with other nitro compounds, indicating Fluorescence Resonance Energy Transfer (FRET) occurred during the quenching process. The emission spectrum of PU and the absorption spectrum of TNP have larger overlap, so that the energy transfer is stronger, the quenching efficiency is obviously improved, and the detection selectivity and sensitivity are improved. As shown in fig. 5b, the uv absorption intensity of PU increases significantly with increasing TNP concentration, but no new absorption peak appears, indicating that there is strong Internal Filtering (IFE) during quenching, but no ground-state charge transfer complex formation.
FIG. 6 is a graph comparing the HOMO/LUMO energy levels of 2, 5-dihydroxyterephthalic acid polyurethane obtained in example 1 of the present invention with various nitroaromatics; the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) energy level diagrams of PU and the nitro compounds show that the LUMO of PU can transfer electrons to the LUMO of TNP, and the existence of the Photoinduced Electron Transfer (PET) between the PU and the LUMO is also the reason of PU fluorescence quenching. However, the PET existing in PU and TNT does not cause fluorescence quenching response of PU to TNT, which indicates that pure PET cannot cause fluorescence quenching of PU, and PET only plays a role in enhancing the effect in the quenching process. In conclusion, three mechanisms exist in the fluorescence quenching process of the TNP by PU, and FRET and IFE account for PET as secondary reasons.
Example 2
Hexamethyldiisocyanate (1.44mmol) was reacted with 2, 5-dihydroxy terephthalic acid (1.11mmol) was added to a 25mL round-bottom flask, and then the end-capping agents polyethylene glycol monomethyl ether (M) were added to the flask separatelyW200) (1.98mmol) and 10mL of catalyst DABCO (12mg) tetrahydrofuran, under the protection of nitrogen and under the anhydrous and oxygen-free conditions, slowly heating to 65 ℃, stirring and refluxing for 8h, cooling to room temperature after the reaction is finished, and precipitating from excessive diethyl ether to obtain a white viscous product, namely the 2, 5-dihydroxy terephthalic acid polyurethane.
The 2, 5-dihydroxyterephthalic acid polyurethane described in example 2 was subjected to1H-NMR and IR spectrum analysis showed that the polyurethane having a structure represented by the formula (1) had Mn of 823g mol based on the analysis results and the kinds of the reaction raw materials-1.
Example 3
Hexamethyldiisocyanate (3.93mmol) and 2, 5-dihydroxyterephthalic acid (2.62mmol) were added to a 25mL round-bottomed flask, and then the blocking agents polyethylene glycol monomethyl ether (M) were added to the flaskW200) (1.98mmol) of catalyst DABCO (12mg) tetrahydrofuran 10mL, under the protection of nitrogen and under the anhydrous and oxygen-free conditions, slowly heating to 65 ℃, stirring and refluxing for 5h, cooling to room temperature after the reaction is finished, and precipitating from excessive diethyl ether to obtain a white viscous product, namely the 2, 5-dihydroxy terephthalic acid polyurethane.
The 2, 5-dihydroxyterephthalic acid polyurethane described in example 3 was subjected to1H-NMR and IR spectroscopy showed that the polyurethane having a structure represented by the formula (1) was obtained from the results of the analyses and the types of the reaction raw materials, and Mn was 689g mol-1.
Example 4
Hexamethyldiisocyanate (2.82mmol) and 2, 5-dihydroxyterephthalic acid (2.02mmol) are added into a 25mL round-bottom flask, and then the end-capping agent polyethylene glycol monomethyl ether (M) is added into the flaskW200) (1.98mmol) and 10mL of catalyst DABCO (12mg) tetrahydrofuran, under the protection of nitrogen and under the anhydrous and oxygen-free conditions, slowly heating to 65 ℃, stirring and refluxing for 8h, cooling to room temperature after the reaction is finished, and precipitating from excessive diethyl ether to obtain a white viscous product, namely the 2, 5-dihydroxy terephthalic acid polyurethane.
2, 5-bis as described in example 4Hydroxyl terephthalic acid polyurethane1H-NMR and IR spectroscopy showed that the polyurethane having the structure shown in formula (1) was obtained from the results of the analyses and the types of the reaction raw materials, and Mn was 740g mol-1.
Example 5
Hexamethyldiisocyanate (4.06mmol) and 2, 5-dihydroxyterephthalic acid (2.62mmol) were added to a 25mL round-bottomed flask, and then the blocking agents polyethylene glycol monomethyl ether (M) were added to the flaskW200) (200) (1.98mmol) and 10mL of catalyst DABCO (12mg) tetrahydrofuran, under the protection of nitrogen and under the anhydrous and oxygen-free conditions, slowly heating to 65 ℃, stirring and refluxing for 8h, cooling to room temperature after the reaction is finished, and precipitating from excessive petroleum ether to obtain a white viscous product, namely the 2, 5-dihydroxy terephthalic acid polyurethane.
The 2, 5-dihydroxyterephthalic acid polyurethane described in example 5 was subjected to1H-NMR and IR spectroscopy showed that the polyurethane having the structure shown in formula (1) was obtained from the results of the analyses and the kinds of the reaction raw materials, and Mn was 873g mol-1.
Example 6
Hexamethyldiisocyanate (4.19mmol) and 2, 5-dihydroxyterephthalic acid (2.62mmol) were added to a 25mL round-bottomed flask, and then the blocking agents polyethylene glycol monomethyl ether (M) were added to the flaskW200)0.396g (1.98mmol) of catalyst DABCO (12mg) tetrahydrofuran 10mL, under the protection of nitrogen, under the anhydrous and oxygen-free conditions, slowly heating to 75 ℃, stirring and refluxing for 6h, cooling to room temperature after the reaction is finished, and precipitating from excessive petroleum ether to obtain a white viscous product, namely the 2, 5-dihydroxy terephthalic acid polyurethane.
The 2, 5-dihydroxyterephthalic acid polyurethane described in example 6 was subjected to1H-NMR and IR spectroscopy showed that the polyurethane having the structure shown in formula (1) was obtained from the results of the analyses and the types of the reaction raw materials, and Mn was 613g mol-1.
Example 72 application of 5, 5-Dihydroxyterephthalic acid polyurethane
Several filter papers (1 cm)2) The PU solution prepared in inventive example 1 (acetonitrile-water 1: 1) then naturally drying at room temperature to form the polyurethaneDetection of ester coating TNP fluorescence quenching sensor. One set of test strips was spotted with a drop of different kinds of nitro compounds (30. mu.M) and the other set of test strips was spotted with 10. mu.L of TNP solutions of different concentrations.
FIG. 7 is a graph showing the effect of the 2, 5-dihydroxy terephthalic acid polyurethane test paper obtained in example 1 on TNP under ultraviolet irradiation.
As shown in fig. 7A, the fluorescence of the test paper rapidly quenched when TNP was dropped on the sensor under 365nm UV irradiation. However, when other nitroaromatics are dropped on the test paper, the test paper still shows strong green fluorescence. The sensor has good selectivity on TNP. As shown in FIG. 7B, different levels of quenching shadows were formed when TNP solutions of different concentrations were dropped onto the test paper, and the lowest concentration of TNP was up to 10-10M。
The 2, 5-dihydroxy terephthalic acid polyurethane disclosed by the invention has the advantages of low price of raw materials, simplicity in synthesis, convenience in use, quick response, low detection limit and the like, and is well applied to detection of explosive TNP.
Claims (7)
- Use of 2, 5-dihydroxyterephthalic acid polyurethane as a fluorescence quenching sensor for detecting explosive 2,4, 6-trinitrophenol, characterized in that M of the 2, 5-dihydroxyterephthalic acid polyurethanen＝600～900g mol-1The structure is shown in a formula 1,
in the formula 1, m represents the repeating number of main repeating units on an oligomer chain, and m is 2.6-4; n represents the repeated number of the polyethylene glycol monomethyl ether part as the end capping agent, and n is 1.3-4.8. - 2. The use of a 2, 5-dihydroxyterephthalic acid polyurethane as a fluorescence quenching sensor for detecting the explosive 2,4, 6-trinitrophenol according to claim 1, wherein the preparation method of the 2, 5-dihydroxyterephthalic acid polyurethane comprises the following steps:under the protection of nitrogen, adding hexamethyl diisocyanate and 2, 5-dihydroxy terephthalic acid into a reaction vessel, then adding a blocking agent, a catalyst and an organic solvent, reacting under anhydrous and anaerobic conditions, cooling to room temperature after the reaction is finished, and precipitating to obtain the 2, 5-dihydroxy terephthalic acid polyurethane.
- 3. The application of the 2, 5-dihydroxy terephthalic acid polyurethane as a fluorescence quenching sensor in detecting explosive 2,4, 6-trinitrophenol according to claim 2, characterized in that the molar ratio of 2, 5-dihydroxy terephthalic acid to hexamethyl diisocyanate is 1 (1.2-1.6).
- 4. The use of the 2, 5-dihydroxyterephthalic acid polyurethane as a fluorescence quenching sensor for detecting 2,4, 6-trinitrophenol as an explosive according to claim 2, wherein the end-capping agent is polyethylene glycol monomethyl ether and the catalyst is triethylene diamine.
- 5. The use of a 2, 5-dihydroxyterephthalic acid polyurethane as a fluorescence quenching sensor for the detection of the explosive 2,4, 6-trinitrophenol according to claim 2, characterized in that the solvent is tetrahydrofuran.
- 6. The use of a 2, 5-dihydroxyterephthalic acid polyurethane as a fluorescence quenching sensor for the detection of the explosive 2,4, 6-trinitrophenol according to claim 2, characterized in that the reaction temperature is 65-75 ℃ and the reaction time is 5-8 h.
- 7. The use of a polyurethane 2, 5-dihydroxyterephthalic acid as a fluorescence quenching sensor for detecting the explosive 2,4, 6-trinitrophenol according to claim 2, characterized in that the molar ratio of the end-capping agent to 2, 5-dihydroxyterephthalic acid is 1: (0.56-1.32).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886626A (en) * | 1987-05-19 | 1989-12-12 | Crest-Foam Corporation | Conductive polyurethane foam compositions containing tetralyanoethylene and method |
| CN101541735A (en) * | 2006-11-28 | 2009-09-23 | 纳幕尔杜邦公司 | Process for the synthesis of 2,5-dihydroxyterephthalic acid |
| CN106380568A (en) * | 2016-08-31 | 2017-02-08 | 四川达威科技股份有限公司 | Waterborne polyurethane and preparation method thereof, and waterborne polyurethane leather filling agent |
| CN107629184A (en) * | 2017-09-26 | 2018-01-26 | 东北师范大学 | A kind of S dinaphthols polyurethane and preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8933189B2 (en) * | 2013-03-15 | 2015-01-13 | E I Du Pont De Nemours And Company | Polymers derived from renewably resourced lysinol |
-
2018
- 2018-09-05 CN CN201811030142.7A patent/CN109337038B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886626A (en) * | 1987-05-19 | 1989-12-12 | Crest-Foam Corporation | Conductive polyurethane foam compositions containing tetralyanoethylene and method |
| CN101541735A (en) * | 2006-11-28 | 2009-09-23 | 纳幕尔杜邦公司 | Process for the synthesis of 2,5-dihydroxyterephthalic acid |
| CN106380568A (en) * | 2016-08-31 | 2017-02-08 | 四川达威科技股份有限公司 | Waterborne polyurethane and preparation method thereof, and waterborne polyurethane leather filling agent |
| CN107629184A (en) * | 2017-09-26 | 2018-01-26 | 东北师范大学 | A kind of S dinaphthols polyurethane and preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| "Aggregation-Induced Long-Lived Phosphorescence in Nonconjugated Polyurethane Derivatives at 77 K";Jiang, Nan; Li et al;《MACROMOLECULES》;20180612;第51卷(第11期);pp:4178-4184 * |
| "Design and high-throughput synthesis of cyclodextrin-based polyurethanes with enhanced molecular recognition properties";Pu Xiao et al;《Polymer Chemistry》;20131231;第4卷(第4期);pp:942-946 * |
| "Selective sensing of 2,4,6-trinitrophenol (TNP) in aqueous media with ‘‘aggregation-induced emission enhancement’’ (AIEE)-active iridium(III) complexes";Che, Weilong et al;《ChemComm》;20180218;第54卷(第14期);pp:1730-1799 * |
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