CN113416329B - Preparation method and application of high-temperature multi-threshold temperature indicating film with fluorescence changing in multiple colors visible to naked eyes - Google Patents
Preparation method and application of high-temperature multi-threshold temperature indicating film with fluorescence changing in multiple colors visible to naked eyes Download PDFInfo
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Abstract
The application discloses a preparation method and application of a high-temperature multi-threshold temperature indicating film with fluorescence multicolor change visible to naked eyes. The individual sample films (in a polymer matrix) are colorless and transparent at room temperature (daylight), and as the temperature increases (uv light), a multi-threshold temperature indication is achieved by a variety of visibly distinct fluorescent color changes, which can be stably maintained for at least five days. Meanwhile, the threshold sensing temperature of different sensing films can be effectively adjusted by changing the polymer matrix with different glass transition temperatures, so that a wide temperature sensing range including a high-temperature region (up to 300 ℃) is achieved.
Description
Technical Field
The invention belongs to the technical field of optical temperature probes, and particularly relates to a preparation method and application of a high-temperature multi-threshold temperature indicating film with fluorescence changing in multiple colors visible to naked eyes.
Background
The temperature is one of the most common physical quantities in daily life, and the diversity of detection modes is concerned by scientific researchers at home and abroad. In most thermometers, such as liquid-in-glass thermometers, thermocouples, and thermistors, sensors ranging in size from tens of micrometers to several millimeters are required for temperature detection. These sensor arrays have the disadvantages of complex fabrication, high cost, and low spatial resolution. The inherent limitations of mechanical or electrical thermometers have prompted the development of optical thermometers for large area or fluid samples. In the existing optical method, an infrared thermometer utilizing the blackbody radiation principle is flexible and easy to use, but can only measure the temperature of the surface, so that the application of the infrared thermometer is limited. Luminescence is one of the most sensitive and easily observable detection signals, and luminescence-based temperature sensors are receiving more and more attention due to their advantages of fast response speed, high spatial resolution, safety in remote operation, and the like. In addition, in practical applications, the luminescence thermometer generally needs to adapt to the surface of the object to be measured in any shape, and the thin film organic luminescence temperature sensor is more advantageous in this respect.
Among the thin film organic light emitting temperature sensors, there are two broad categories, instantaneous thermal sensing and threshold temperature sensing. Studies have shown that high temperature threshold temperature sensors are important for detecting damage to building materials, measuring the surface temperature of aerospace components, and recording the maximum temperature of infrastructure after a fire. Moreover, with the rapid development of modern industrial technologies, in order to ensure production safety, the surface temperature of the production environment or production facility components needs to be monitored, and an early warning signal is sent out under a high-temperature condition. Therefore, it is necessary to obtain an organic thin film state threshold temperature indicator suitable for use in a high temperature environment. However, some organic threshold temperature sensors invented at present generally have the defects of poor film forming property, low threshold temperature, complex preparation process, discontinuous luminescence and the like.
Therefore, we have synthesized triaryl phosphorus oxide compounds with more heat resistance: (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphine oxide (PZ1) and bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphine oxide (PZ 2). And mixing the fluorescent powder with polymer matrixes with different glass transition temperatures to prepare a series of high-temperature threshold temperature sensors capable of observing fluorescent color change by naked eyes. The series of high-temperature threshold temperature sensors have the advantages of good film forming property, simple preparation, high detection temperature (up to 300 ℃), various fluorescent color changes and the like.
Disclosure of Invention
The technical problem to be solved is as follows: in order to overcome the defects in the prior art, the application provides a preparation method and application of a high-temperature multi-threshold temperature indicating film with fluorescence changing in a multicolor manner visible to naked eyes, and aims to solve the technical problems of complex manufacture, high cost, low spatial resolution, poor film forming property, low threshold temperature, complex preparation process, discontinuous luminescence and the like in the prior art.
The technical scheme is as follows:
a method for preparing a high-temperature multi-threshold temperature indicating film with fluorescence changing in multiple colors visible to naked eyes comprises the following steps:
the first step is as follows: synthesizing two triaryl phosphorus oxygen compounds (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenyl phosphorus oxide (PZ1) and bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) with high temperature resistance through addition reaction, then extracting an organic phase, purifying the organic phase by using a gel chromatography technology, and finally spin-drying and vacuum-drying the mixed solution by using a spin-steaming device to obtain an organic luminescent dye for later use;
the second step is that: according to the organic luminescent dye: weighing organic luminescent dye and polymer matrix according to the mass part ratio of 100, and blending and dissolving in a chromatographic dichloromethane solution environment to obtain a mixed solution;
the third step: dripping the mixed solution on a quartz chip substrate by a dripping method to form a film;
the fourth step: standing and then drying; thus, the preparation of PZ1/PS, PZ1/PMMA, PZ1/PC, PZ1/PEES, PZ2/PS, PZ2/PMMA, PZ2/PC and PZ2/PEES films is completed.
As a preferred embodiment of the present application, the organic light emitting materials are named (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphinic oxide (PZ1) and bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphine oxide (PZ2), respectively, and have the following structural formulas:
as a preferred technical solution of the present application, a preparation method of the organic luminescent material PZ1 is:
s1, weighing required solid medicines, namely 1, 6-dibromopyrene (13.9mmol), phenothiazine (15.29mmol), sodium tert-butoxide (11.12mmol) and a catalyst, namely bis (dibenzylideneacetone) palladium (0.695mmol) by using an accurate balance, pouring into a reaction bottle, adding 150ml of toluene and tri-tert-butylphosphine (1.39mmol), reacting under the nitrogen protection environment, heating to 80 ℃, and reacting for 12 hours; after the reaction is finished, extracting by dichloromethane, adding silica gel powder, removing filtrate by rotary evaporation, then sampling, separating by column chromatography to obtain light yellow solid powder to obtain 2.98g yellow solid 10- (6-bromopyran-1-yl) -10H phenothiazine, wherein the reaction formula is
S2, adding 10- (6-bromopyran-1-yl) -10H phenothiazine (2.09mmol) into a reaction bottle, blowing nitrogen, sealing, dropwise adding the distilled THF solution into the reaction bottle, adding dry ice (0.5Kg) and acetone (1L) into a heat preservation sleeve, measuring the temperature in the heat preservation sleeve after ten minutes, reducing the temperature to-78 ℃, adding n-BuLi (2.3mmol), stirring at the stirring speed of 1000rpm for reaction for 1 hour, naturally heating to room temperature, continuously stirring for 1 hour, reducing the temperature to-78 ℃ again, adding diphenyl phosphorus chloride (2.5mmol), and stirring for 6 hours; finally, 10ml of methanol was added to quench H2O2(10ml, 30%) was added dropwise to the mixed reaction solution, stirred overnight, the next day, the organic phase was extracted with dichloromethane and evaporated, the crude product was purified by column chromatography after removal of the filtrate by rotary evaporation to give 0.60g of PZ1 (48% yield) according to the formula
As a preferred technical solution of the present application, a preparation method of the organic luminescent material PZ2 is:
s1, weighing required solid medicines, namely 1, 6-dibromopyrene (13.9mmol), phenothiazine (15.29mmol), sodium tert-butoxide (11.12mmol) and a catalyst, namely bis (dibenzylideneacetone) palladium (0.695mmol) by using an accurate balance, pouring into a reaction bottle, adding 150ml of toluene and tri-tert-butylphosphine (1.39mmol), reacting under the nitrogen protection environment, heating to 80 ℃, and reacting for 12 hours; after the reaction is finished, extracting by dichloromethane, adding silica gel powder, removing filtrate by rotary evaporation, then sampling, separating by column chromatography to obtain light yellow solid powder to obtain 2.98g yellow solid 10- (6-bromopyran-1-yl) -10H phenothiazine, wherein the reaction formula is
S2, adding 10- (6-bromopyran-1-yl) -10H phenothiazine (2.09mmol) into a reaction bottle, sealing after blowing nitrogen, dropwise adding the distilled THF solution into the reaction bottle, adding dry ice (0.5Kg) and acetone (1L) into a heat preservation sleeve, measuring the temperature in the heat preservation sleeve after ten minutes, reducing the temperature to-78 ℃, adding n-BuLi (2.3mmol), stirring at the stirring speed of 1000rpm for reaction for 1 hour, naturally heating to room temperature, continuously stirring for 1 hour, reducing the temperature to-78 ℃, adding phenyl phosphorus dichloride (1mmol), stirring at the stirring speed of 1000rpm for 6 hours, finally adding 10ml methanol for quenching, and quenching H2O2(10ml, 30%) was added dropwise to the mixed reaction solution, stirred overnight, the next day, the organic phase was extracted with dichloromethane and the filtrate was removed by rotary evaporation, and the crude product was purified by column chromatography to obtain 0.41g of PZ2 (yield: 43%) as a reaction formula
As a preferred technical scheme of the application: the polymer matrix is one or more of polystyrene PS, polymethyl methacrylate (PMMA), Polycarbonate (PC) and poly (1, 4-phenylene ether sulfone) (PEES), and the glass transition temperature T of the PS, the PMMA, the PC and the PEESgCorresponding to 100 deg.C, 105 deg.C, 135 deg.C and 221 deg.C, respectively.
As a preferred technical scheme of the application: when the polymer matrix is PS or PC, the color change of a plurality of kinds of luminescence with temperature dependence observable by naked eyes is in a wide temperature range, so that a plurality of temperature thresholds are indicated, and the luminescence has irreversibility and stability.
As a preferred technique of the present applicationThe technical scheme is as follows: when the polymer matrix is several of PS, PMMA, PC and PEES, different T is formed in the film by changinggThe polymer matrix can realize a temperature sensing system with adjustable threshold temperature by using macroscopic luminescent color change, and the adjustable threshold temperature can reach 300 ℃ at most.
The application also discloses an application of the naked eye visible fluorescence multicolor-change high-temperature multi-threshold temperature indicating film prepared by the preparation method in a temperature sensor.
Has the advantages that:
1. the invention is based on the heat-resistant organic luminescent material with the triaryl phosphorus-oxygen structure and the polymer matrix with different glass transition temperatures, has simple synthesis steps, and prepares a series of easy-to-operate high-temperature multi-threshold temperature indicating films with naked eye visible multicolor change through simple co-dissolution and drop coating.
2. The series of thin film temperature indicators has a high threshold temperature indication (up to 300 c).
3. A single thin film threshold temperature indicator has multiple temperature dependent color changes visible to the naked eye, enabling multiple threshold temperature sensing.
4. The controllability of the threshold temperature of the thin film can be achieved by varying the polymer matrix with different glass transition temperatures.
5. The luminescent color of the film has irreversibility and stability at high temperature, and can be applied for a long time.
6. The series of threshold temperature sensors are good in film forming property, simple in preparation mode and excellent in flexibility, and can be coated on objects in any shapes to realize real-time temperature monitoring.
Drawings
FIG. 1 is a graph showing a temperature-dependent luminescence spectrum of a (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphine oxide (PZ1) and Polystyrene (PS) blended film in example 2 of the present application.
FIG. 2 is a graph showing a temperature-dependent luminescence spectrum of a (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphinic oxide (PZ1) and polymethyl methacrylate (PMMA) blended film in example 3 of the present application.
FIG. 3 is a graph showing a temperature-dependent luminescence spectrum of a (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphinic oxide (PZ1) and Polycarbonate (PC) blended film in example 4 of the present application.
FIG. 4 is a graph showing a temperature-dependent luminescence spectrum of a film obtained by blending (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphinic oxide (PZ1) and poly-1, 4-phenylene ether sulfone (PEES) in example 5 of the present application.
FIG. 5 is a photograph showing luminescence at different temperatures of a blended film system of (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphine oxide (PZ1) with PS (polystyrene), PC (polycarbonate) and PEES (poly-1, 4-phenylene ether sulfone), respectively, in example 6 of the present application.
FIG. 6 is a graph showing a temperature-dependent luminescence spectrum of a blend film of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) and Polystyrene (PS) in example 7 of the present application.
FIG. 7 is a graph showing a temperature-dependent luminescence spectrum of a blend film of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) and polymethyl methacrylate (PMMA) in example 8 of the present application.
FIG. 8 is a graph showing a temperature-dependent luminescence spectrum of a blend film of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) and Polycarbonate (PC) in example 9 of the present application.
FIG. 9 is a graph showing a temperature-dependent luminescence spectrum of a film of a blend of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) and poly-1, 4-phenylene ether sulfone (PEES) in example 10 of the present application.
FIG. 10 is a photograph of light emission at different temperatures of thin film blends of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) with PS (polystyrene), PC (polycarbonate) and PEES (poly-1, 4-phenylene ether sulfone), respectively, in example 11 of this application.
FIG. 11 is a graph showing a luminescence spectrum of a blended film of (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphinic oxide (PZ1) and Polystyrene (PS) in example 2 of this application, which was continuously monitored for five days after it was heated to 140 ℃ and cooled to room temperature.
FIG. 12 is a graph showing a luminescence spectrum of a blended film of (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenylphosphinic oxide (PZ1) and Polystyrene (PS) in example 2 of the present application, which was continuously monitored for five days after it was heated to 200 ℃ and cooled to room temperature.
FIG. 13 is a graph showing a luminescence spectrum of a blend film of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) and Polystyrene (PS) in example 7 of this application, which was continuously monitored for five days after heating to 140 ℃ and cooling to room temperature.
FIG. 14 is a graph showing a luminescence spectrum of a blend film of bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2) and Polystyrene (PS) in example 7 of this application, which was continuously monitored for five days after heating to 200 ℃ and cooling to room temperature.
Detailed Description
The application discloses a preparation method and application of a high-temperature multi-threshold temperature indicating film with fluorescence changing in multicolor visible to naked eyes, and relates to organic luminescent materials, wherein the names of the organic luminescent materials are (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenyl phosphorus oxide (PZ1) and bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide (PZ2), and the structural formulas are as follows:
the preparation method of the organic luminescent material PZ1 comprises the following steps:
s1, weighing required solid medicines, namely 1, 6-dibromopyrene (13.9mmol), phenothiazine (15.29mmol), sodium tert-butoxide (11.12mmol) and a catalyst, namely bis (dibenzylideneacetone) palladium (0.695mmol) by using an accurate balance, pouring into a reaction bottle, adding 150ml of toluene and tri-tert-butylphosphine (1.39mmol), reacting under the nitrogen protection environment, heating to 80 ℃, and reacting for 12 hours; after the reaction is finished, extracting by dichloromethane, adding silica gel powder, removing filtrate by rotary evaporation, then loading, and separating by column chromatography to obtain light yellow solid powder to obtain 2.98g yellow solid 10- (6-bromopyran-1-yl) -10H phenothiazine;1HNMR(400MHz,CDCl3)δ8.57(d,J＝9.2Hz,1H),8.45(d,J＝8.0Hz,1H),8.34(d,J＝9.1Hz,1H),8.28(dd,J＝8.8,3.9Hz,2H),8.15(d,J＝8.1Hz,1H),8.04(dd,J＝8.6,7.0Hz,2H),7.07(dd,J＝6.2,2.8Hz,2H),6.78(dd,J＝8.5,6.4Hz,2H),6.67(t,J＝7.5Hz,2H),5.93(s,2H)；
the reaction formula is as follows:
s2, adding 10- (6-bromopyran-1-yl) -10H phenothiazine (2.09mmol) into a reaction bottle, blowing nitrogen, sealing, dropwise adding the distilled THF solution into the reaction bottle, adding dry ice (0.5Kg) and acetone (1L) into a heat preservation sleeve, measuring the temperature in the heat preservation sleeve after ten minutes, reducing the temperature to-78 ℃, adding n-BuLi (2.3mmol), stirring at the stirring speed of 1000rpm for reaction for 1 hour, naturally heating to room temperature, continuously stirring for 1 hour, reducing the temperature to-78 ℃ again, adding diphenyl phosphorus chloride (2.5mmol), and stirring for 6 hours; finally, 10ml of methanol was added to quench H2O2(10ml, 30%) was added dropwise to the mixed reaction solution, stirred overnight, the next day, the organic phase was extracted with dichloromethane and evaporated, the crude product was purified by column chromatography after removal of the filtrate by rotary evaporation to give 0.60g of PZ1 (48% yield);1H NMR(400MHz,CDCl3)δ9.09(d,J＝9.2Hz,1H),8.46(t,J＝8.8Hz,2H),8.16(dd,J＝8.7,6.0Hz,2H),8.11–8.04(m,2H),7.81(dd,J＝13.0,6.8Hz,1H),7.75(dd,J＝12.1,7.1Hz,4H),7.59(t,J＝6.9Hz,2H),7.50(t,J＝6.1Hz,4H),7.08(dd,J＝7.6,1.5Hz,2H),6.80(t,J＝7.0Hz,2H),6.71–6.66(m,2H),5.95(d,J＝7.3Hz,2H).MALDI-TOF m/z:599.2[M]+.HRMS(EI)m/z:599.1467[M]+.Anal.Calcd for C40H26NOPS(599.1473)。
the reaction formula is as follows:
the preparation method of the organic luminescent material PZ2 comprises the following steps:
s1, weighing the required solid drugs 1, 6-dibromopyrene (13.9mmol), phenothiazine (15.29mmol), sodium tert-butoxide (11.12mmol) and a catalyst palladium bis (dibenzylideneacetone) (0.695mmol) by using an accurate balance, pouring into a reaction bottle, adding 150ml of toluene and the catalyst palladium bis (dibenzylideneacetone) (0.695mmol)Reacting tri-tert-butylphosphine (1.39mmol) under the nitrogen protection environment, heating to 80 ℃, and reacting for 12 h; after the reaction is finished, extracting by dichloromethane, adding silica gel powder, removing filtrate by rotary evaporation, then loading, and separating by column chromatography to obtain light yellow solid powder to obtain 2.98g yellow solid 10- (6-bromopyran-1-yl) -10H phenothiazine;1H NMR(400MHz,CDCl3)δ8.57(d,J＝9.2Hz,1H),8.45(d,J＝8.0Hz,1H),8.34(d,J＝9.1Hz,1H),8.28(dd,J＝8.8,3.9Hz,2H),8.15(d,J＝8.1Hz,1H),8.04(dd,J＝8.6,7.0Hz,2H),7.07(dd,J＝6.2,2.8Hz,2H),6.78(dd,J＝8.5,6.4Hz,2H),6.67(t,J＝7.5Hz,2H),5.93(s,2H)；
the reaction formula is as follows:
s2, adding 10- (6-bromopyran-1-yl) -10H phenothiazine (2.09mmol) into a reaction bottle, sealing after blowing nitrogen, dropwise adding the distilled THF solution into the reaction bottle, adding dry ice (0.5Kg) and acetone (1L) into a heat preservation sleeve, measuring the temperature in the heat preservation sleeve after ten minutes, reducing the temperature to-78 ℃, adding n-BuLi (2.3mmol), stirring at the stirring speed of 1000rpm for reaction for 1 hour, naturally heating to room temperature, continuously stirring for 1 hour, reducing the temperature to-78 ℃, adding phenyl phosphorus dichloride (1mmol), stirring at the stirring speed of 1000rpm for 6 hours, finally adding 10ml methanol for quenching, and quenching H2O2(10ml, 30%) was added dropwise to the mixed reaction solution, stirred overnight, the next day, the organic phase was extracted with dichloromethane and the filtrate was removed by rotary evaporation, and the crude product was purified by column chromatography to give 0.41g of PZ2 (yield: 43%);1H NMR(400MHz,CDCl3)δ9.31(d,J＝9.8Hz,1H),8.48–8.42(m,2H),8.18–8.13(m,2H),8.04(t,J＝9.8Hz,2H),7.77(dd,J＝18.0,7.2Hz,2H),7.63–7.58(m,1H),7.51(d,J＝2.4Hz,1H),7.06(d,J＝8.5Hz,2H),6.79(d,J＝2.7Hz,2H),6.68(t,J＝8.9Hz,2H),5.94(d,J＝7.8Hz,2H).MALDI-TOF m/z:920.4[M]+.HRMS(EI)m/z:920.2079[M]+.Anal.Calcd for C62H37N2OPS2(920.2085)。
the reaction formula is as follows:
example 1:
a method for preparing a high-temperature multi-threshold temperature indicating film (0.5 wt% PZ 1/polymer or 0.5 wt% PZ 2/polymer film) with fluorescence multicolor change visible to naked eyes comprises the following steps:
the first step is as follows: preparing triaryl phosphorus-oxygen structure compound PZ1 or PZ2 according to the method;
the second step is that: adding a polymer matrix material (one of PS, PMMA, PC and PEES) which is colorless and transparent, easy to mold and process and good in thermal stability and fluidity during melting into a reagent bottle, then adding a chromatographic dichloromethane solvent for dissolving, then adding a triaryl phosphorus oxygen structure compound PZ1 or PZ2 according to the proportion of 0.5 wt% (the mass of the compound accounts for 0.5% of the total mass of the compound and the polymer matrix), and performing ultrasonic treatment to completely dissolve the compound to obtain a mixed solution;
the third step: dripping the mixed solution on a quartz chip substrate at room temperature by using a dripping method to form a film;
the fourth step: standing, and then drying in a vacuum drying oven until the solvent is completely volatilized; namely, the preparation of the high-temperature multi-threshold temperature sensing film PZ1/PS, PZ1/PMMA, PZ1/PC, PZ1/PEES, PZ2/PS, PZ2/PMMA, PZ2/PC or PZ2/PEES is completed.
Example 2:
the temperature-dependent luminescence property test was carried out on a 0.5% wt PZ1/PS film.
For films with PZ1 mixed with PS (PZ1/PS), the change in the emission spectrum of the film was relatively insignificant as the temperature was increased from 30 ℃ to 80 ℃. In the temperature range of 100 ℃ to 140 ℃, the organic luminescent molecule PZ1 is partially depolymerized in the film due to reaching the glass transition temperature of PS, the emission peak intensities of the monomers at 390nm and 420nm are increased, and the emission peak of the aggregate (excimer) at 525nm is rapidly reduced. The luminous intensity of the film is greatly enhanced, and obvious conversion on the luminous color also occurs. As the temperature is further increased from 140 ℃ to 300 ℃, the absolute fluorescence intensity emitted by the monomer decreases rapidly, since the phenomenon of the high temperature promoting an increase in non-radiative decay is dominant compared to the depolymerization effect. However, the film at this time still maintained the macroscopic luminous intensity. In the whole heating interval (30-300 ℃), the luminescent spectrum presents temperature-dependent proportional emission characteristics, and the obvious change of luminescent color along with the temperature change is ensured. By taking fluorescent photographs of the film at different temperatures, it was found that: between 30 ℃ and 200 ℃, the PZ1/PS film undergoes multicolor emissions of white-green, bluish-white, sky-blue and deep-blue, corresponding to 30 ℃, 120 ℃, 140 ℃ and 200 ℃, respectively. By heating the PZ1/PS to 140 ℃ and 200 ℃ respectively, then slowly cooling to room temperature and continuing monitoring of the luminescence spectrum, it was found that the spectrum remained stable at high temperature (140 ℃ or 200 ℃) and could be maintained for at least five days.
Example 3:
a temperature-dependent luminescence property test was carried out on a 0.5% wt PZ1/PMMA film.
For the film with PZ1 mixed with PMMA (PZ1/PMMA), as the temperature increases from 30 ℃ to 300 ℃, the monomer peak (set of peaks around 380nm and 400 nm) emission of the film emission spectrum gradually increases and the aggregate emission peak (around 527 nm) gradually decreases. When 100 ℃ is reached (close to the T of PMMA)g) The monomer peak emission has a relatively obvious enhancement phenomenon. Within the whole heating interval of 30-300 ℃, the luminescence spectrum presents temperature-dependent proportional emission characteristics.
Example 4:
the temperature dependent luminescence property test was performed on a 0.5% wt PZ1/PC film.
For the film with PZ1 mixed with PC (PZ1/PC), heating from 30 to 300 ℃ gradually increases the intensity of the absolute emission of the monomer (around 435 nm), while the intensity of the absolute emission of the excimer (around 545 nm) continues to decrease. Within the whole heating interval of 30-300 ℃, the luminescence spectrum presents temperature-dependent proportional emission characteristics, and the obvious change of luminescence color along with the temperature change is ensured. By taking fluorescent photographs of the film at different temperatures, we found that: between 30 ℃ and 300 ℃, the PZ1/PC film undergoes a polychromatic emission of white green, light blue and sky blue, corresponding to 30 ℃, 200 ℃ and 260 ℃, respectively.
Example 5:
the temperature-dependent luminescence property test was carried out on a 0.5% wt PZ1/PEES film.
For the film with PZ1 mixed with PEES (PZ1/PEES), heating from 30 to 300 ℃, the absolute emission intensity of the monomer (around 440 nm) gradually increases, while the absolute emission intensity of the excimer (around 560 nm) continues to decrease. Within the whole heating interval of 30-300 ℃, the luminescence spectrum presents temperature-dependent proportional emission characteristics, and the obvious change of luminescence color along with the temperature change is ensured. By taking fluorescent photographs of the film at different temperatures, we found that: between 30 ℃ and 300 ℃, the PZ1/PEES film undergoes a light green to light blue fluorescence color change, corresponding to 30 ℃ and 260 ℃, respectively.
Example 6:
the specific design of the 0.5 wt% PZ 1/polymer film with adjustable threshold is as follows:
the PZ1/PS, PZ1/PC and PZ1/PEES films with obvious luminescence are respectively placed on the same heating table, the fluorescence colors of different films are changed in different colors when the temperature is increased from 30 ℃ to 300 ℃ under a 365nm ultraviolet lamp, and the corresponding threshold temperature is changed along with the doped polymer TgIs increased, thereby realizing the regulation of the threshold temperature (up to 260 ℃).
Example 7:
the temperature-dependent luminescence property test was carried out on a 0.5% wt PZ2/PS film.
For the film with mixed PZ2 and PS (PZ2/PS), the monomer emission peak is roughly around 450nm and the excimer emission peak is around 560nm at room temperature. Similar to the temperature-dependent luminescence spectrum of the PZ1/PS film, the aggregate absolute emission intensity of the PZ2/PS film gradually decreases and the monomer absolute emission intensity gradually increases as the temperature increases from 30 ℃ to 140 ℃, and the monomer emission intensity gradually decreases between 140 ℃ and 300 ℃ due to the fact that the thermally-promoted non-radiative decay becomes the dominant factor. From the fluorescence photographs taken, the PZ2/PS film underwent color changes of dark green, bluish white, light blue and sky blue between 30 ℃ and 240 ℃ corresponding to 30 ℃, 120 ℃, 160 ℃ and 240 ℃, respectively. By heating the PZ2/PS to 140 ℃ and 200 ℃ respectively, then slowly cooling to room temperature and continuing monitoring of the luminescence spectrum, it was found that the spectrum remained stable at high temperature (140 ℃ or 200 ℃) and could be maintained for at least five days.
Example 8:
a temperature-dependent luminescence property test was carried out on a 0.5% wt PZ2/PMMA film.
For a film (PZ2/PMMA) formed by mixing PZ2 and PMMA, as the temperature is increased from 30 ℃ to 300 ℃, the monomer peak (a group of peaks around 438 nm) emission of the emission spectrum of the film is gradually increased, the aggregate emission peak (around 540 nm) is gradually reduced, and the emission spectrum shows temperature-dependent proportional emission characteristics within the whole heating interval of 30-300 ℃.
Example 9:
the 0.5 wt% PZ2/PC high temperature multi-threshold temperature sensing film in this example was subjected to a temperature dependent luminescence property test.
For the film with PZ2 mixed with PC (PZ2/PC), heating from 30 to 300 ℃ gradually increases the intensity of the absolute emission of the monomer (around 450 nm), while the intensity of the absolute emission of the excimer (around 560 nm) continues to decrease. Within the whole heating interval of 30-300 ℃, the luminescence spectrum presents temperature-dependent proportional emission characteristics, and the obvious change of luminescence color along with the temperature change is ensured. By taking fluorescent photographs of the film at different temperatures, we found that: between 30 ℃ and 300 ℃, the PZ2/PC film undergoes a multicolor emission of yellow, yellow-white, blue-white, corresponding to 30 ℃, 160 ℃, 300 ℃ respectively.
Example 10:
the temperature-dependent luminescence property test was carried out on a 0.5% wt PZ2/PEES film.
For the film with PZ2 mixed with PEES (PZ2/PEES), heating from 30 to 300 ℃ does not result in a significant change in the absolute emission intensity of the monomer (around 440 nm), while the absolute emission intensity of the excimer (around 565 nm) continues to decrease. Within the whole heating interval of 30-300 ℃, the luminescence spectrum presents temperature-dependent proportional emission characteristics, and the obvious change of luminescence color along with the temperature change is ensured. By taking fluorescent photographs of the film at different temperatures, we found that: between 30 ℃ and 300 ℃, the PZ2/PEES film undergoes a change in emission color from yellow-green to blue-white, corresponding to 30 ℃ and 300 ℃, respectively.
Example 11:
the specific design of the 0.5 wt% PZ 2/polymer film with adjustable threshold temperature is as follows:
the PZ2/PS, PZ2/PC and PZ2/PEES films with obvious luminescence are respectively placed on the same heating table, the fluorescence colors of different films are changed in different colors when the temperature is increased from 30 ℃ to 300 ℃ under a 365nm ultraviolet lamp, and the corresponding threshold temperature is changed along with the doped polymer TgIs increased, thereby realizing the regulation of the threshold temperature (up to 300 ℃).
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. The preparation method of the high-temperature multi-threshold temperature indicating film with fluorescence multicolor change visible to naked eyes is characterized by comprising the following steps:
the first step is as follows: synthesizing two triaryl phosphorus oxide compounds with high-temperature resistance (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenyl phosphorus oxide PZ1 and bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide PZ2 through addition reaction, then extracting an organic phase, purifying the organic phase by using a gel chromatography technology, and finally spin-drying and vacuum-drying the mixed solution by using a spin-steaming device to obtain an organic luminescent dye for later use; the (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenyl phosphorus oxide PZ1 and bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide PZ2 have the following structural formulas:
the second step is that: according to the organic luminescent dye: weighing organic luminescent dye and polymer matrix according to the mass part ratio of 100, and blending and dissolving in a chromatographic dichloromethane solution environment to obtain a mixed solution; the polymer matrix is one or more of polystyrene PS, polymethyl methacrylate (PMMA), Polycarbonate (PC) and poly (1, 4-phenylene ether sulfone) (PEES), and the glass transition temperature T of the PS, the PMMA, the PC and the PEESgRespectively corresponding to 100 ℃, 105 ℃, 135 ℃ and 221 ℃;
the third step: dripping the mixed solution on a quartz chip substrate by a dripping method to form a film;
the fourth step: standing and then drying; thus, the preparation of PZ1/PS, PZ1/PMMA, PZ1/PC, PZ1/PEES, PZ2/PS, PZ2/PMMA, PZ2/PC and PZ2/PEES films is completed.
2. The preparation method of the naked eye visible fluorescence multicolor-changing high-temperature multi-threshold temperature indicating film according to claim 1, characterized in that: the preparation method of the (6- (10H-phenothiazin-10-yl) pyrene-1-yl) diphenyl phosphorus oxide PZ1 comprises the following steps:
s1, weighing 13.9mmol of needed solid medicine 1, 6-dibromopyrene, 15.29mmol of phenothiazine, 11.12mmol of sodium tert-butoxide and 0.695mmol of catalyst bis (dibenzylideneacetone) palladium by using an accurate balance, pouring into a reaction bottle, adding 150ml of toluene and 1.39mmol of tri-tert-butylphosphine, reacting under the nitrogen protection environment, heating to 80 ℃, and reacting for 12 hours; after the reaction is finished, extracting by dichloromethane, adding silica gel powder, removing filtrate by rotary evaporation, then sampling, and separating by column chromatography to obtain light yellow solid powder to obtain 2.98g yellow solid 10- (6-bromopyran-1-yl) -10H phenothiazine, wherein the reaction formula is as follows:
s2, adding 2.09mmol of 10- (6-bromopyran-1-yl) -10H phenothiazine into a reaction bottle, blowing nitrogen, sealing, dropwise adding a distilled THF solution into the reaction bottle, adding 0.5Kg of dry ice and 1L of acetone into a heat preservation sleeve, measuring the temperature in the heat preservation sleeve after ten minutes, reducing the temperature to-78 ℃, adding n-BuLi 2.3mmol, stirring at the stirring speed of 1000rpm for reaction for 1 hour, naturally heating to room temperature, continuously stirring for 1 hour, reducing the temperature to-78 ℃, adding 2.5mmol of diphenyl phosphorus chloride, and stirring for 6 hours; finally, quench with 10ml methanol and 30% H2O210ml of the reaction mixture was added dropwise to the mixture, stirred overnight the next day, the organic phase was extracted with dichloromethane and evaporated, the crude product was purified by column chromatography after removal of the filtrate by rotary evaporation to give 0.60g of PZ1 in 48% yield according to the formula:
3. the preparation method of the naked eye visible fluorescence multicolor-changing high-temperature multi-threshold temperature indicating film according to claim 1, characterized in that: the preparation method of the bis (6- (10H-phenothiazin-10-yl) pyrene-1-yl) (phenyl) phosphorus oxide PZ2 comprises the following steps:
s1, weighing 13.9mmol of needed solid medicine 1, 6-dibromopyrene, 15.29mmol of phenothiazine, 11.12mmol of sodium tert-butoxide and 0.695mmol of catalyst bis (dibenzylideneacetone) palladium by using an accurate balance, pouring into a reaction bottle, adding 150ml of toluene and 1.39mmol of tri-tert-butylphosphine, reacting under the nitrogen protection environment, heating to 80 ℃, and reacting for 12 hours; after the reaction is finished, extracting by dichloromethane, adding silica gel powder, removing filtrate by rotary evaporation, then sampling, and separating by column chromatography to obtain light yellow solid powder to obtain 2.98g yellow solid 10- (6-bromopyran-1-yl) -10H phenothiazine, wherein the reaction formula is as follows:
s2, 10- (6-bromopyran-1-yl) -10H phenothiazine 2.09mmol is added into a reaction bottle, nitrogen is blown into the reaction bottle, the reaction bottle is sealed, the distilled THF solution is dropwise added into the reaction bottle, 0.5Kg of dry ice and 1L of acetone are added into a heat preservation sleeve, the temperature in the heat preservation sleeve is measured to be reduced to-78 ℃ after ten minutes, n-BuLi 2.3mmol is added, the reaction is stirred for 1 hour under the stirring speed of 1000rpm, the temperature is naturally increased to the room temperature, the temperature is reduced to-78 ℃ after the continuous stirring for 1 hour, phenyl phosphorus dichloride 1mmol is added, the reaction is stirred for 6 hours under the stirring speed of 1000rpm, finally, 10ml of methanol is added for quenching, 30 percent H phenothiazine 2.09mmol is added into the reaction bottle, nitrogen is blown into the reaction bottle, the reaction bottle is sealed, the reaction bottle is filled with n-BuLi 2.3mmol, the reaction bottle is filled with the reaction bottle, the reaction bottle is naturally heated to be naturally, the reaction bottle is cooled to be 1 hour, the reaction bottle is cooled to be cooled2O210ml of the reaction mixture was added dropwise, stirred overnight the next day, the organic phase was extracted with dichloromethane and the filtrate removed by rotary evaporation and the crude product was purified by column chromatography to give 0.41g of PZ2, yield: 43%, the reaction formula is:
4. the preparation method of the naked eye visible fluorescence multicolor-changing high-temperature multi-threshold temperature indicating film according to claim 1, characterized in that: when the polymer matrix is one of PS or PC, the single film has a plurality of temperature-dependent changes of luminescence colors which are observable by naked eyes in a wide temperature range, thereby indicating a plurality of temperature thresholds, and the luminescence has irreversibility and stability.
5. The preparation method of the naked eye visible fluorescence multicolor-changing high-temperature multi-threshold temperature indicating film according to claim 1, characterized in that: when the polymer matrix is several of PS, PMMA, PC and PEES, the temperature sensing system with adjustable threshold temperature consisting of a plurality of films is realized by using macroscopic luminescent color change, and the adjustable threshold temperature can reach 300 ℃ at most.
6. The application of the high-temperature multi-threshold temperature indicating film with fluorescence changing in multiple colors visible to naked eyes prepared by the preparation method of claim 1 in a temperature sensor.
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