CN112299965A - Tetraphenyl ethylene-based material and method for detecting temperature and organic solvent steam - Google Patents
Tetraphenyl ethylene-based material and method for detecting temperature and organic solvent steam Download PDFInfo
- Publication number
- CN112299965A CN112299965A CN202011018441.6A CN202011018441A CN112299965A CN 112299965 A CN112299965 A CN 112299965A CN 202011018441 A CN202011018441 A CN 202011018441A CN 112299965 A CN112299965 A CN 112299965A
- Authority
- CN
- China
- Prior art keywords
- organic solvent
- temperature
- film
- substrate
- based material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
- C07C323/02—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/03—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
- G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a tetraphenyl vinyl material and a method for detecting temperature and organic solvent steam, wherein the tetraphenyl vinyl material provided by the invention is a halogenated chain hydrocarbon substituent-containing tetraphenyl vinyl material, and the luminescent color of the tetraphenyl vinyl material is changed when the temperature and the organic solvent steam change, so that the tetraphenyl vinyl material is used for detecting the temperature and the organic solvent steam, and the method has the advantages that: the adopted tetraphenyl vinyl material has the advantages of simple chemical structure, easy acquisition, environmental protection, green, low toxicity, high sensitivity to temperature and organic solvent vapor, no need of large-scale instruments and equipment for detection, extremely low cost, quick process and simple operation; by means of the change of the color of the film material, the change of multiple temperature sections can be detected, and the organic solvent can be detected, so that the method is suitable for the practical application in laboratories or production workshops in chemical engineering and biological medical treatment.
Description
Technical Field
The invention relates to the technical field of materials for detecting temperature and organic solvent steam, and particularly belongs to a tetraphenyl ethylene-based material and a method for detecting temperature and organic solvent steam.
Background
The chemical industry or the biological medicine industry is often accompanied by high temperature and dissipation of organic solvent in the production process, and it is worth noting that the temperature and the solvent not only waste energy, but also pose certain threats to production safety. Currently, means of temperature detection mainly focus on physical methods, such as medical thermometers, which vary in density with temperature according to the change in mercury or alcohol; the industrial thermocouple or the thermal resistor is different mainly according to different temperature influences of metal resistors such as nickel, rhodium and the like, the physical detection methods usually need special equipment, the manufacturing cost is high, and even if the manufacturing cost of the temperature is low, safe and convenient, the temperature change can be detected only singly, and whether organic solvent steam exists in the environment cannot be detected. Therefore, it is very important to develop an effective, simple and feasible method for detecting temperature and organic solvent simultaneously.
The detection methods of temperature and organic solvents are mainly based on the development of core materials. First, the core material for temperature and organic solvent detection should have the characteristics of solid fluorescence, as analyzed from the practical point of view. Secondly, if the detection of temperature and organic solvent is realized, the solid-state fluorescence emission is only one of the necessary properties of the material, and more importantly, the material also needs to have the light-emitting property (color, intensity and the like) which changes along with the change of the external environment. Such materials must then have the activity of multiple stimuli responses, i.e. the colour of the luminescence of the material changes from one to another under the influence of temperature or solvents, as analyzed from a technical point of view. Thirdly, the temperature required in the production of chemical engineering or biological medicine is higher (100-200 ℃). Therefore, the required material must have a certain resistance to high temperatures. It follows that the core material for temperature and organic solvent detection must meet the above three requirements.
In combination with organic photoelectric materials, researchers in recent years report a material with very excellent properties, namely tetraphenyl ethylene derivatives, and the material can form a solid-state influence characteristic with higher luminous efficiency because a certain torsion angle can be formed inside molecules containing a polyaromatic ring structure to prevent the self-quenching accumulation formation of the molecules and effectively inhibit non-radiative transition. In addition, modification of the functional group of the tetraphenylethenyl group is effective for achieving stimulus-responsive activity. In summary, it is necessary and feasible to develop a method for detecting temperature and organic solvent by using a group-modified tetraphenylethylene material.
Disclosure of Invention
The invention aims to provide a tetraphenyl vinyl material and a method for detecting temperature and organic solvent steam, which overcome the defects of the prior art.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a tetraphenyl vinyl material is characterized in that the chemical structural formula is as follows:
wherein R is1、R2、R3、R4Is one of 3-halopropanoxy or 3-halopropanmercapto.
Preferably, the halogen in the 3-halopropane oxy is one of fluorine, chlorine, bromine and iodine, and the halogen in the 3-halopropane mercapto is one of fluorine, chlorine, bromine and iodine.
Preferably, the method for preparing the tetraphenyl vinyl material comprises the following steps: dissolving raw materials 4,4 '-tetraphenol-1, 1,2, 2-ethylene or 4,4' -tetramercapto-1, 1,2, 2-ethylene and sodium carbonate or sodium carbonate in a solvent, adding 1, 3-dihalopropane under stirring, heating and refluxing the mixed solution after nitrogen protection, cooling the reaction mixture to room temperature after the reaction is finished, washing out inorganic salts, extracting to obtain a mother solution, removing the solvent from the mother solution to obtain a crude product, and separating and purifying the crude product to obtain the target product tetraphenylethylene-based material.
Preferably, the halogen in the 1, 3-dihalogenopropane is one of fluorine, chlorine, bromine and iodine.
The application of tetraphenyl vinyl material in temperature and organic solvent vapor detection.
The application method of the tetraphenyl vinyl material in temperature and organic solvent vapor detection comprises the following steps:
step 1, dissolving a tetraphenyl vinyl material in a mixed solvent, and recrystallizing at 25-40 ℃ to obtain a solid sample;
step 2, dissolving a solid sample in a dissolving agent to prepare a precursor solution of 0.05-0.15 mol/mL;
step 3, coating 20-35 mL of precursor solution on a substrate, standing at 30-50 ℃ for 3-6 min to volatilize the solvent, and drying to obtain the substrate with the film; and repeatedly coating for 3-5 times to enable the thickness of the film to reach 0.05-0.9 mm, then placing the substrate covered with the film at 25-35 ℃, blowing by nitrogen flow for 20-40 min to fully volatilize the solvent to obtain the substrate containing the tetraphenyl ethylene material film, and then irradiating by using ultraviolet light to observe that the luminescent color of the film is blue-green.
Step 4, placing the substrate obtained in the step 3 in an environment of 85-95 ℃ for 4-7 min, and irradiating by using ultraviolet light to observe that the luminescent color of the film is dark blue;
step 5, raising the temperature of the substrate in the step 4 to 135-145 ℃, carrying out irradiation for 3-5 min, and observing that the luminescent color of the film is blue-green by using ultraviolet light;
step 6, placing the substrate obtained in the step 5 in an organic solvent steam environment for 1-3 s at 25-35 ℃, and irradiating by using ultraviolet light to observe that the luminescent color of the film is dark blue; and continuously standing for 3-4 min, and irradiating by using ultraviolet light to observe that the luminescent color of the film is blue-green.
Preferably, the wavelength of the ultraviolet light is 365 nm.
Preferably, the mixed solvent is a mixture of dichloromethane and ethanol or n-hexane, and the volume ratio is 1-4.
Preferably, the dissolving agent is at least one of ethanol, dichloromethane, tetrahydrofuran and methanol.
Preferably, the concentration of the organic solvent steam is 1-20 ppm.
Preferably, the organic solvent is at least one of n-hexane, toluene, diethyl ether, ethanol, acetone, dichloromethane, ethyl acetate, tetrahydrofuran, methanol, pyridine and dimethyl sulfoxide.
Preferably, the substrate is one of glass, polyimide resin, ceramic and metal.
Preferably, the CIE1931XYZ color space coordinate of the film with the blue-green light emitting color is (0.16,0.20) - (0.16, 0.25).
Preferably, the CIE1931XYZ color space coordinate of the film with the blue light emission color is (0.16,0.12) to (0.16, 0.17).
Compared with the prior art, the invention has the following implementation effects:
firstly, through a fluorescence emission spectrum test of a material film, firstly, when the material film is heated at 85-95 ℃, the maximum emission wavelength of the emission spectrum is blue-shifted from 466-478 nm to 410-416 nm; further heating to 135-145 ℃, and red-shifting the maximum emission wavelength of an emission spectrum from 410-417 nm to 470-478 nm; placing the material film in a steam environment with the concentration of an organic solvent of 1-20 ppm, and blue-shifting the maximum emission wavelength of an emission spectrum from 466-470 nm to 411-416 nm; further fumigating, and shifting the maximum emission wavelength of the emission spectrum from 410-415 nm to 470-478 nm. The emission spectrum data fully verifies that the film prepared by the material has detection effect on temperature and organic solvent.
Secondly, by means of the irradiation of ultraviolet light, the change of the color of the substrate film can be observed by naked eyes, and the change range of the environmental temperature and the existence of organic solvent steam can be detected quickly and conveniently.
Thirdly, the preparation method of the material is simple, green and environment-friendly, an effective detection method of temperature and organic solvent vapor is obtained through a simple film preparation technology on a glass substrate, the method is scientific and reasonable, the technology is feasible, the operation is simple and easy to master, the detection effect is rapid and obvious to naked eyes, large and expensive instruments and equipment are not needed, the detection cost is extremely low, the process is rapid, and the operation is simple; by means of the change of the color of the film material, the change of multiple temperature sections can be detected, and the organic solvent can be detected, so that the method is suitable for the practical application in laboratories or production workshops in chemical engineering and biological medical treatment.
As a further embodiment of the beneficial effects, the substrate is preferably a polyimide resin substrate, and the substrate can be further processed into a flexible substrate besides the characteristic of high temperature resistance, thereby being beneficial to manufacturing a wearable thin-film device.
The color change principle of the material of the invention is as follows: the tetraphenyl vinyl material contains four benzene rings per molecule, and the benzene ring structures can form molecular conformations with larger torsion angles in the process of crystallization from an organic solvent, and in addition, the chain hydrocarbon structures contained in the molecules can further promote the molecular packing to be in a loose state. When the material is subjected to external stimuli (mechanical grinding, organic solvent fumigation and heating), the torsion angle of molecules and the stacking state between molecules are changed, so that the charge distribution in the molecules is changed, and macroscopic color change is generated.
Drawings
FIG. 1 is a graph showing the change in luminescence color of 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after heating and fumigation with an organic solvent;
FIG. 2 is a fluorescence emission spectrum of the 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after heating at a temperature of 90 ℃;
FIG. 3 is a CIE1931XYZ color space coordinate change after heating the 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate at a temperature of 90 ℃ in example 9;
FIG. 4 is a fluorescence emission spectrum of the 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after heating at a temperature of 140 ℃;
FIG. 5 is a CIE1931XYZ color space coordinate change of a 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after heating at a temperature of 140 ℃;
FIG. 6 is a fluorescence emission spectrum of 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after fumigating with an organic solvent for 1 s;
FIG. 7 is a CIE1931XYZ color space coordinate change of 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after fumigating 1s with an organic solvent;
FIG. 8 is a fluorescence emission spectrum of the 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after 3min of organic solvent fumigation;
FIG. 9 is a CIE1931XYZ color space coordinate change of 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene material coated on a polyimide flexible substrate in example 9 after 3min of organic solvent vapor fumigation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The sources of the starting materials 4,4 '-tetraphenol-1, 1,2, 2-ethylene, 4' -tetramercapto-1, 1,2, 2-ethylene were obtained commercially during the experiments.
Example 1
The starting materials 4,4' -tetraphenol-1, 1,2, 2-ethylene (0.50g) and sodium carbonate (1.83g) were dissolved in a tetrahydrofuran solution (30mL), and 1, 3-difluoropropane (2.02g) was added thereto under stirring, and the mixture was heated to 80 ℃ under nitrogen protection and refluxed for 15 hours. After the reaction is finished, the reaction mixture is also cooled to room temperature, inorganic salts are removed by water washing, a mother liquor is obtained by using dichloromethane solvent extraction, and a crude product is obtained by using a rotary evaporator to remove organic solvents. And (3) carrying out column chromatography separation and purification on the crude product, and eluting by using a mixed solvent of dichloromethane and n-hexane with a volume ratio of 4:1 to finally obtain a target product 1,1,2, 2-tetra (4- (3-chloropropoxy) phenyl) ethylene material. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.01–4.03(m,8H,4-CH2),3.60–3.57(m,8H,4-CH2),2.31–2.25(m,8H,4-CH2) The synthesized product was confirmed to be:
example 2
The starting materials 4,4' -tetraphenol-1, 1,2, 2-ethylene (0.50g) and sodium carbonate (1.61g) were dissolved in a tetrahydrofuran solution (30mL), and 1, 3-dichloropropane (2.34g) was added under stirring to stir the mixture, and after nitrogen protection, the mixture was heated to 43 ℃ for reflux reaction for 11 hours. After the reaction is finished, the reaction mixture is also cooled to room temperature, inorganic salts are removed by water washing, a mother liquor is obtained by using dichloromethane solvent extraction, and a crude product is obtained by using a rotary evaporator to remove organic solvents. Subjecting the crude product to column chromatography for separation and purification, and mixing dichloromethane and n-hexane at a volume ratio of 4:1Eluting with a solvent to finally obtain the target product 1,1,2, 2-tetra (4- (3-chloropropoxy) phenyl) ethylene material. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.06–4.09(m,8H,4-CH2),3.60–3.57(m,8H,4-CH2),2.30–2.23(m,8H,4-CH2) The synthesized product was confirmed to be:
example 3
The starting materials 4,4' -tetraphenol-1, 1,2, 2-ethylene (0.50g) and potassium carbonate (1.79g) were dissolved in a tetrahydrofuran solution (30mL), and 1, 3-dibromopropane (2.59g) was added thereto under stirring, and the mixture was refluxed at 70 ℃ for 12 hours under nitrogen protection. After the reaction is finished, the reaction mixture is also cooled to room temperature, inorganic salts are removed by water washing, a mother liquor is obtained by using dichloromethane solvent extraction, and a crude product is obtained by using a rotary evaporator to remove organic solvents. And (3) carrying out column chromatography separation and purification on the crude product, and eluting by using a mixed solvent of dichloromethane and n-hexane with a volume ratio of 3:1 to finally obtain the target product 1,1,2, 2-tetra (4- (3-bromopropoxy) phenyl) ethylene material. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.0–4.02(m,8H,4-CH2),3.60–3.57(m,8H,4-CH2),2.31–2.25(m,8H,4-CH2) The synthesized product was confirmed to be:
example 4
The starting materials 4,4' -tetraphenol-1, 1,2, 2-ethylene (0.50g) and potassium carbonate (1.96g) were dissolved in a tetrahydrofuran solution (30mL), and 1, 3-diiodopropane (2.76g) was added thereto under stirring, and after nitrogen protection of the mixed solution, the mixture was heated to 60 ℃ for reflux reaction for 14 hours. After the reaction is finished, the reaction mixture is cooled to room temperature and washed out by waterRemoving inorganic salt, extracting with dichloromethane solvent to obtain mother liquor, and removing organic solvent with rotary evaporator to obtain crude product. And (3) carrying out column chromatography separation and purification on the crude product, and eluting by using a mixed solvent of dichloromethane and n-hexane with a volume ratio of 2:1 to finally obtain the target product 1,1,2, 2-tetra (4- (3-iodopropoxy) phenyl) ethylene material. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.05–4.09(m,8H,4-CH2),3.60–3.57(m,8H,4-CH2),2.32–2.26(m,8H,4-CH2) The synthesized product was confirmed to be:
example 5
The difference from example 1 is that 0.5g of 4,4 '-tetraphenol-1, 1,2, 2-ethylene is replaced by 0.70g of 4,4' -tetramercapto-1, 1,2, 2-ethylene. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.01–4.03(m,8H,4-CH2),3.61–3.56(m,8H,4-CH2),2.31–2.25(m,8H,4-CH2) The synthesized product was confirmed to be:
example 6
The difference from example 2 is that 0.5g of 4,4 '-tetraphenol-1, 1,2, 2-ethylene is replaced by 0.70g of 4,4' -tetramercapto-1, 1,2, 2-ethylene. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.06–4.09(m,8H,4-CH2),3.61–3.56(m,8H,4-CH2),2.30–2.23(m,8H,4-CH2) The synthesized product was confirmed to be:
example 7
The difference from example 3 is that 0.5g of 4,4',4 ", 4'" -tetraphenol-1, 1,2, 2-ethylene was replaced by 4,4',4 ", 4'" -tetramercapto-1, 1,2, 2-ethylene 0.70g and the product structure was characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.0–4.02(m,8H,4-CH2),3.61–3.56(m,8H,4-CH2),2.31–2.25(m,8H,4-CH2) The synthesized product was confirmed to be:
example 8
The difference from example 4 was that 0.5g of 4,4 '-tetraphenol-1, 1,2, 2-ethylene was replaced by 0.70g of 4,4' -tetramercapto-1, 1,2, 2-ethylene. The product structure is characterized as:1H NMR(400MHz,CDCl3,ppm)δ6.93–6.91(m,8H,ArH),6.65–6.63(m,8H,ArH),4.05–4.09(m,8H,4-CH2),3.61–3.56(m,8H,4-CH2),2.32–2.26(m,8H,4-CH2) The synthesized product was confirmed to be:
example 9
Step 1, dissolving 1,1,2, 2-tetrakis (4- (3-fluoropropoxy) phenyl) ethylene prepared in example 1 in a dichloromethane/ethanol solution with a volume ratio of 1, and recrystallizing at 25 ℃ to obtain a solid sample;
step 2, dissolving the solid sample in ethanol, and preparing a precursor solution with the concentration of 0.05mol/L for the preparation of a coating film in the next step;
step 3, dropwise adding 20mL of precursor coating liquid on a polyimide substrate, slowly drying at 42 ℃ for 3min, and volatilizing the solvent; after the film was dried, the coating was repeated 3 times to make the film thickness 0.05mm, and the substrate covered with the film was placed at 25 ℃ under a nitrogen flow for 20min to sufficiently volatilize the solvent to obtain a polyimide substrate containing a 1,1,2, 2-tetrakis (4- (3-bromopropoxy) phenyl) ethylene film, and then irradiated with 365nm ultraviolet light, and the film was observed to emit blue-green as shown in FIG. 1.
Step 4, placing the substrate obtained in the step 3 in an environment at 90 ℃ for 5min, and irradiating with 365nm ultraviolet light, wherein the luminescent color of the film is dark blue as observed in fig. 1, the maximum emission wavelength of the emission spectrum is shifted from 466nm blue to 410nm as shown in fig. 2, and the CIE1931XYZ color space coordinate is (0.16,0.14) as shown in fig. 3;
step 5, raising the temperature of the environment where the substrate is located in the step 4 to 140 ℃ for 3min, and irradiating with 365nm ultraviolet light, wherein the luminescent color of the film is blue-green as observed in figure 1, the maximum emission wavelength of the emission spectrum of figure 4 is shifted from 410nm red to 470nm, and the CIE1931XYZ color space coordinate of figure 5 is (0.16, 0.25);
step 6, placing the substrate obtained in the step 5 in an ethanol steam environment, wherein the concentration is 2ppm, the temperature is 25 ℃, the time is 1s, and then irradiating by 365nm ultraviolet light, wherein the luminescent color of the film is dark blue as observed in fig. 1, the maximum emission wavelength of the emission spectrum of fig. 6 is blue shifted from 466nm to 411nm, and the CIE1931XYZ color space coordinate of fig. 7 is (0.16, 0.14);
and 7, continuously placing the substrate obtained in the step 6 in an ethanol steam environment, wherein the concentration is 2ppm, the temperature is 25 ℃, the time is 3min, irradiating by 365nm ultraviolet light, observing that the luminescent color of the film is blue-green as shown in the figure 1, and shifting the maximum emission wavelength of the emission spectrum from 410nm to 470nm as shown in the figure 8, wherein the CIE1931XYZ color space coordinate is (0.16,0.25) as shown in the figure 9.
Example 10
Step 1, dissolving 1,1,2, 2-tetra (4- (3-bromopropoxy) phenyl) ethylene prepared in example 3 in a dichloromethane/n-hexane solution with a volume ratio of 2, and recrystallizing at 30 ℃ to obtain a solid sample;
step 2, dissolving the solid sample in tetrahydrofuran, and preparing a precursor solution with the concentration of 0.1mol/L for the preparation of a coating film in the next step;
step 3, dropwise adding 30mL of precursor coating liquid on the polyimide substrate, slowly drying at 50 ℃ for 3.5min, and volatilizing the solvent; after the film is dried, the film is repeatedly coated for 4 times to enable the thickness of the film to reach 0.75mm, the substrate covered with the film is placed at 30 ℃ for nitrogen flow blowing for 30min to enable the solvent to be fully volatilized, the polyimide substrate containing the 1,1,2, 2-tetra (4- (3-bromopropoxy) phenyl) ethylene film is obtained, then 365nm ultraviolet light is used for irradiating, and the luminous color of the film is observed to be blue-green.
Step 4, placing the substrate obtained in the step 3 in an environment at 95 ℃ for 6min, irradiating the substrate by 365nm ultraviolet light, observing that the luminescent color of the film is dark blue, the maximum emission wavelength of an emission spectrum is blue-shifted from 468nm to 413nm, and the CIE1931XYZ color space coordinate is (0.16, 0.15);
step 5, raising the temperature of the environment where the substrate is located in the step 4 to 135 ℃ for 4min, irradiating by 365nm ultraviolet light, observing that the luminescent color of the film is blue-green, the maximum emission wavelength of an emission spectrum is red-shifted from 413nm to 465nm, and the CIE1931XYZ color space coordinate is (0.16, 0.23);
step 6, placing the substrate obtained in the step 5 in a dichloromethane steam environment, wherein the concentration is 5ppm, the temperature is 30 ℃, the time is 2s, irradiating by 365nm ultraviolet light, observing that the luminescent color of the film is dark blue, the maximum emission wavelength of an emission spectrum is shifted from 465nm blue to 413nm, and the CIE1931XYZ color space coordinate is (0.16 );
and 7, continuously placing the substrate obtained in the step 6 in a dichloromethane steam environment, wherein the concentration is 5ppm, the temperature is 30 ℃, the time is 4min, irradiating by 365nm ultraviolet light, observing that the luminescent color of the film is blue-green, the maximum emission wavelength of an emission spectrum is red-shifted from 413nm to 467nm, and the CIE1931XYZ color space coordinate is (0.16, 0.22).
In addition, it was found through experiments that the detection methods and results as shown in fig. 1, fig. 2, fig. 3, fig. 4, fig. 5, fig. 6, fig. 7, fig. 8 and fig. 9 can be similarly obtained by repeating the above examples 9 to 10 while changing the product purification solvent ratio, the precursor solution concentration, the drying temperature for preparing the thin film, the thickness of the thin film, the number of times of thin film coating repetition, the solvent removal fumigation time, the kind of the substrate, and the temperature and time of the thin film heating environment, and using the vapor concentration and fumigation time of any one of n-hexane, toluene, diethyl ether, ethanol, acetone, dichloromethane, ethyl acetate, tetrahydrofuran, methanol, pyridine, and dimethylsulfoxide.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A tetraphenyl vinyl material is characterized in that the chemical structural formula is as follows:
wherein R is1、R2、R3、R4Is one of 3-halopropanoxy or 3-halopropanmercapto.
2. The tetraphenylethylene-based material of claim 1, wherein the halogen in the 3-halopropanoxy group is one of fluorine, chlorine, bromine and iodine, and the halogen in the 3-halopropanmercapto group is one of fluorine, chlorine, bromine and iodine.
3. Use of the tetraphenyl vinyl material of claim 1 or 2 in temperature and organic solvent vapor detection.
4. The method for using the tetraphenyl vinyl material of claim 1 or 2 in temperature and organic solvent vapor detection, comprising the steps of:
step 1, dissolving tetraphenyl vinyl material in a mixed solvent for recrystallization to obtain a solid sample;
step 2, dissolving the solid sample in a dissolving agent to prepare a precursor solution;
step 3, coating the precursor solution on a substrate, volatilizing the solvent, and drying to obtain a substrate with a thin film; and repeatedly coating to enable the thickness of the film to reach 0.05-0.9 mm, then placing the substrate covered with the film in nitrogen flow to blow and blow so as to enable the solvent to be fully volatilized, obtaining the substrate containing the tetraphenyl ethylene material film, and then irradiating by using ultraviolet light to observe that the luminescent color of the film is blue-green.
Step 4, placing the substrate obtained in the step 3 in an environment of 85-95 ℃ for 4-7 min, and irradiating the substrate with ultraviolet light to observe that the luminescent color of the film is dark blue;
step 5, raising the temperature of the substrate in the step 4 to 135-145 ℃, carrying out irradiation for 3-5 min, and observing that the luminescent color of the film is blue-green;
step 6, placing the substrate obtained in the step 5 in an organic solvent steam environment for 1-3 s at 25-35 ℃, and irradiating by using ultraviolet light to observe that the luminescent color of the film is dark blue; and continuously standing for 3-4 min, and irradiating by using ultraviolet light to observe that the luminescent color of the film is blue-green.
5. The method for using the tetraphenylethylene-based material in temperature and organic solvent vapor detection according to claim 4, wherein the wavelength of the ultraviolet light is 365 nm.
6. The method for applying the tetraphenylethylene based material in temperature and organic solvent vapor detection according to claim 4, wherein the mixed solvent is a mixture of dichloromethane and ethanol or n-hexane.
7. The method for using the tetraphenylethylene based material in temperature and organic solvent vapor detection according to claim 4, wherein the dissolving agent is at least one of ethanol, dichloromethane, tetrahydrofuran, and methanol.
8. The application method of the tetraphenylethylene-based material in temperature and organic solvent vapor detection according to claim 4, characterized in that the concentration of the organic solvent vapor is 1-20 ppm.
9. The method for applying the tetraphenylethylene based material in temperature and organic solvent vapor detection according to claim 4, wherein the organic solvent is at least one of n-hexane, toluene, diethyl ether, ethanol, acetone, dichloromethane, ethyl acetate, tetrahydrofuran, methanol, pyridine, and dimethylsulfoxide.
10. The method for applying the tetraphenylethylene-based material in temperature and organic solvent vapor detection according to claim 4, wherein the substrate is one of glass, polyimide resin, ceramic and metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011018441.6A CN112299965B (en) | 2020-09-24 | 2020-09-24 | Tetraphenyl ethylene-based material and method for detecting temperature and organic solvent steam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011018441.6A CN112299965B (en) | 2020-09-24 | 2020-09-24 | Tetraphenyl ethylene-based material and method for detecting temperature and organic solvent steam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112299965A true CN112299965A (en) | 2021-02-02 |
| CN112299965B CN112299965B (en) | 2022-11-22 |
Family
ID=74489193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011018441.6A Active CN112299965B (en) | 2020-09-24 | 2020-09-24 | Tetraphenyl ethylene-based material and method for detecting temperature and organic solvent steam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112299965B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461546A (en) * | 2021-07-27 | 2021-10-01 | 华中科技大学 | Steric hindrance type tetraphenyl ethylene spirochete capable of emitting deep blue fluorescence and synthetic method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120172296A1 (en) * | 2005-04-22 | 2012-07-05 | The Hong Kong University Of Science And Technology | Water-soluble aie luminogen for monitoring and retardation of amyloid fibrillation of insulin |
| CN102706839A (en) * | 2011-01-31 | 2012-10-03 | 香港科技大学 | Water-soluble aie illuminant and purpose of the illuminant in detecting and delaying starch sample fibering of starch sample protein |
| CN103772203A (en) * | 2014-01-24 | 2014-05-07 | 武汉大学 | Nucleic acid fluorescence probe and preparation method thereof |
| CN105874319A (en) * | 2013-12-03 | 2016-08-17 | 香港科技大学 | Specific detection and quantification of cardiolipin and isolated mitochondria by positively charged AIE fluorogens and method of manufacturing of AIE fluorogens |
| CN108088825A (en) * | 2017-11-30 | 2018-05-29 | 华南理工大学 | A kind of fluorescent chemicals and its synthetic method for formaldehyde examination and the application in Ratio-type fluorescent test paper |
| CN108586290A (en) * | 2018-07-09 | 2018-09-28 | 北京师范大学 | A kind of amido substitution tetraphenyl ethylene derivative and preparation method thereof and the purposes in terms of gas detection |
-
2020
- 2020-09-24 CN CN202011018441.6A patent/CN112299965B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120172296A1 (en) * | 2005-04-22 | 2012-07-05 | The Hong Kong University Of Science And Technology | Water-soluble aie luminogen for monitoring and retardation of amyloid fibrillation of insulin |
| CN102706839A (en) * | 2011-01-31 | 2012-10-03 | 香港科技大学 | Water-soluble aie illuminant and purpose of the illuminant in detecting and delaying starch sample fibering of starch sample protein |
| CN105874319A (en) * | 2013-12-03 | 2016-08-17 | 香港科技大学 | Specific detection and quantification of cardiolipin and isolated mitochondria by positively charged AIE fluorogens and method of manufacturing of AIE fluorogens |
| CN103772203A (en) * | 2014-01-24 | 2014-05-07 | 武汉大学 | Nucleic acid fluorescence probe and preparation method thereof |
| CN108088825A (en) * | 2017-11-30 | 2018-05-29 | 华南理工大学 | A kind of fluorescent chemicals and its synthetic method for formaldehyde examination and the application in Ratio-type fluorescent test paper |
| CN108586290A (en) * | 2018-07-09 | 2018-09-28 | 北京师范大学 | A kind of amido substitution tetraphenyl ethylene derivative and preparation method thereof and the purposes in terms of gas detection |
Non-Patent Citations (3)
| Title |
|---|
| XING-HUO WANG等: "Efficient Aggregation-Induced Emission Manipulated by Polymer Host Materials", 《ADV. MATER.》 * |
| YIFAN DONG等: "Investigating the effects of side chain length on the AIE properties of water-soluble TPE derivatives", 《TETRAHEDRON LETTERS》 * |
| 张玉才: "四苯乙烯在固态下的荧光性能探究", 《南通职业大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461546A (en) * | 2021-07-27 | 2021-10-01 | 华中科技大学 | Steric hindrance type tetraphenyl ethylene spirochete capable of emitting deep blue fluorescence and synthetic method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112299965B (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Tb-MOF: a naked-eye and regenerable fluorescent probe for selective and quantitative detection of Fe 3+ and Al 3+ ions | |
| CN112299965B (en) | Tetraphenyl ethylene-based material and method for detecting temperature and organic solvent steam | |
| CN108947766B (en) | Fluorine-containing tetraphenylethylene compound and preparation method and application thereof | |
| CN105732623A (en) | Preparation method of reduction-state ionic salt of perylene bisimide and derivative thereof | |
| CN107759504B (en) | Dual-phase organic fluorescent material with strong fluorescence in solid and liquid states and preparation method thereof | |
| Tao et al. | Tuning aggregation-induced emission properties with the number of cyano and ester groups in the same dibenzo [b, d] thiophene skeleton for effective detection of explosives | |
| JP2013173726A (en) | Coumarin derivative | |
| CN104961746B (en) | Quinoid near infrared fluorescent compound and its preparation method and application | |
| CN106188152A (en) | A kind of near-infrared metal complex and preparation thereof and application | |
| CN105158219B (en) | A kind of method using the boron ester compounds detection peroxide containing aldehyde radical | |
| CN113480739B (en) | Supermolecule polymer containing two-axis chiral structure and preparation method and application thereof | |
| WO2019173243A1 (en) | Polycyclic aromatic compounds and methods for making and using the same | |
| CN110759890A (en) | Nopinanyl indazole silver ion fluorescent probe and preparation method thereof | |
| CN115286646A (en) | Probe for detecting amine compound residue in polyurethane, preparation method and application thereof | |
| CN111559989B (en) | Synthesis method and application of visible light-promoted 2-aminonaphtho [2,1-d ] thiazole compound | |
| CN110872303A (en) | Compound containing spiro acridine structure and application thereof | |
| Zhang et al. | An Optic/Proton Dual‐Controlled Fluorescence Switch based on Novel Photochromic Bithienylethene Derivatives | |
| CN107162929A (en) | A kind of detection copper ion and the probe and preparation method of zinc ion and application | |
| CN111073633B (en) | Naphthalene ring thiophenol fluorescent probe | |
| CN109053815B (en) | Iridium (III) complex and preparation method and application thereof | |
| CN108558595B (en) | P-phenylene ethylene bridged trimer indene derivative and preparation method thereof | |
| CN107602456B (en) | Azopyridine salt compound and preparation method thereof | |
| CN113321671A (en) | Boron dipyrromethene solid-state luminescent material, preparation method and application thereof, and blue light driven LED | |
| Fan et al. | Synthesis of novel phenylazo-substituted salicylaldimine-based boron difluoride complexes | |
| CN110161000A (en) | A kind of identification Hg2+、Ag+Dianthranide derivatives fluorescent probe and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |