CN112362189A - Preparation method of flexible transparent temperature sensor - Google Patents
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Abstract
The invention relates to the field of sensors and discloses a preparation method of a flexible transparent temperature sensor. The temperature sensitive characteristic that the volume can generate mutation near the lower critical phase transition temperature (LCST) is utilized; and has the advantages of no hysteresis, good biocompatibility, soft hand feeling, high comfort level and the like.
Description
Technical Field
The invention relates to the field of sensors, in particular to a preparation method of a flexible transparent temperature sensor.
Background
With the popularization of intelligent terminals, wearable electronic equipment presents huge development prospects. The flexible electronic sensor has the characteristics of lightness, thinness, good biocompatibility and the like, and is widely concerned. Research on flexible wearable sensors currently focuses on pressure, gas and humidity, and there is less relevant research on flexible temperature sensors. Temperature has been widely noticed by people as an important index for measuring physiological information and environmental conditions of human bodies.
The traditional flexible temperature sensor adopts olefins such as polyethylene, high-density polyethylene and the like as substrates, and further industrial application and popularization of the conductive composite material are severely limited. In recent years, although flexible temperature sensors manufactured by different processes have high sensitivity and good stretchability, the performance of the flexible temperature sensors is still different from that of the traditional temperature sensors, and the flexible temperature sensors are high in cost and complicated in manufacturing process.
The silver nanowires keep the excellent flexibility and light transmittance of metal silver, and the elastic conductor made of the silver nanowires has the characteristics of simple manufacturing process, expandability, excellent electric conductivity, good transparency and high corrosion resistance.
PDMS is a high molecular organic silicon compound, has high chemical stability, good insulativity, excellent adhesiveness, low material cost, simple manufacture and use, good light transmission and good biocompatibility, and can be widely used in the field of microelectronics. The solid PDMS is non-toxic, non-flammable, good in light transmission and high in flexibility and elasticity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a flexible transparent temperature sensor, which selects PDMS as a substrate, silver nanowires as conductive filling materials and polymethacrylate(s) as temperature-sensitive materials, wherein the PDMS has good transparency, chemical stability and excellent thermal expansion, and the silver nanowires have excellent conductivity and good flexibility. The temperature sensitive characteristic that the volume can generate mutation near the lower critical phase transition temperature (LCST) is utilized; and has the advantages of no hysteresis, good biocompatibility, soft hand feeling, high comfort level and the like.
The specific technical scheme of the invention is as follows: a preparation method of a flexible transparent temperature sensor comprises the following steps:
(1) preparation of poly (N, N-dimethylaminoethyl methacrylate): vacuumizing and filling nitrogen for several times in a polymerization tube, taking 2-chloropropionic acid propinyl ester as an initiator, and reacting cuprous chloride catalyst and N, N-dimethylaminoethyl methacrylate according to a mass ratio of 0.5-0.7: 0.1: 90-110 are added into the ethanol solution in sequence, and finally Me accounting for 1-2 percent of the total mass of the raw materials is added6Cyclam and ATRP initiators (Me)6The mass ratio of Cyclam to ATRP initiator is 1: 2) heating to react, cooling to room temperature after the reaction is finished, taking out a product, dissolving the product in THF, purifying by neutral alumina column chromatography, rotationally evaporating the solvent, and drying in vacuum to obtain a colorless viscous solid, namely the poly (N, N-dimethylaminoethyl methacrylate).
The polymerization process has controllable activity, and can synthesize polymer with low dispersity and determined molecular weight and molecular structure.
(2) Adding the poly N, N-dimethylaminoethyl methacrylate into the ethanol solution, and stirring to obtain the poly N, N-dimethylaminoethyl methacrylate solution.
(3) Preparing a silver nanowire solution: adding polyvinylpyrrolidone into ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, and then adding ferric chloride solution and stirring uniformly; then transferring the obtained mixed solution into a reaction kettle, dropwise adding a silver nitrate solution (the mass ratio of ferric chloride to silver nitrate is 1: 4-6) into the mixed solution when the temperature is raised to 145-155 ℃), fully stirring, then reacting for 4-8 h at 155-165 ℃, cooling to room temperature after the reaction is completed, then transferring the reaction solution into a centrifuge tube, and carrying out centrifugal washing by using ethanol; and finally, pouring out the supernatant, adding the obtained silver nanowire precipitate into absolute ethyl alcohol, and performing ultrasonic dispersion to form a silver nanowire solution.
(4) And mixing the silver nanowire solution with the poly N, N-dimethylaminoethyl methacrylate solution, and ultrasonically stirring to obtain a mixed solution.
(5) Then, PDMS and methylene chloride were added to the mixed solution and stirred uniformly.
Prevent the solution from forming colloid in advance during the stirring process to influence the dispersibility of the material, and add dichloromethane to maintain the fluidity of the solution. The dichloromethane was completely volatilized during the stirring.
(6) Adding octamethylcyclotetrasiloxane curing agent accounting for 5-15% of the mass of PDMS, ultrasonically stirring, and placing the obtained mixed solution into a vacuum furnace to remove bubbles.
The different thicknesses of the PDMS film have an influence on the tensile property of the film, and further influence the surface characteristics of the conductive composite material and the flexibility and the conductive stability of the conductive film. Therefore, the thickness of the film needs to be controlled to be 1-2mm, and the prepared film has higher requirement on the uniformity of the thickness of the film, so a spin coater is selected for spin coating.
(7) Transferring the mixed solution to a coating substrate, coating the mixed solution by using a spin coater to form a coating film, controlling the thickness of the film to be 1-2mm, and heating at constant temperature;
(8) and drying and curing the obtained coating, peeling off the coating from the coated substrate to prepare a film, and adhering copper foils on two sides of the film to obtain the flexible transparent temperature sensor.
Preferably, in the step (1), the polymerization tube is filled with nitrogen for 3-5 times, an ATRP initiator with alkynyl at the tail end is selected, the reaction temperature is 70-80 ℃, and the reaction time is 4-6 h.
Preferably, in step (1), tetrahydrofuran is selected as eluent for neutral alumina column chromatography, and vacuum drying is carried out at 40-60 ℃ for 24-30 h.
Preferably, in the step (2), the stirring time is 20 to 40min, and the concentration of the poly (N, N-dimethylaminoethyl methacrylate) solution is 15 to 30 wt%.
Preferably, in the step (3), the mass ratio of the polyvinylpyrrolidone to the ethylene glycol is 2: 95-105; the centrifugal speed is 3000-; the concentration of the silver nanowire solution is 1-3 mg/ml.
Preferably, in the step (4), the mass ratio of the poly N, N-dimethylaminoethyl methacrylate to the silver nanowires is 1: 2-10.
Preferably, in the step (5), the dosage ratio of the total amount of the PDMS and the dichloromethane to the mixed solution is 8-12:1, the dosage ratio of the PDMS to the dichloromethane is 100:2-4, and the stirring time is 30-50 min.
Preferably, in the step (6), the ultrasonic stirring time is 40-60min, and the degassing time is 0.5-1 h.
Preferably, in the step (7), the spin speed of the spin coater is 400-600rpm, the heating temperature is 60-70 ℃, and the constant temperature heating time is 3-5 h.
Preferably, in the step (8), the drying curing temperature is 75-85 ℃, and the curing time is 4-6 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention utilizes the electrochemical sensitivity of the silver nanowires and the temperature sensitivity of the polymethyl methacrylate N, N-dimethyl aminoethyl methacrylate, and the product responds sensitively to external force.
(2) The invention adopts polymethyl N, N-dimethyl amino ethyl acrylate as temperature sensitive material, and the product has good transparency.
(3) The invention adopts the poly N, N-dimethylaminoethyl methacrylate and the PDMS, thereby ensuring that the product has good biocompatibility.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Preparation of poly (N, N-dimethylaminoethyl methacrylate): after evacuating and charging nitrogen gas 5 times in a polymerization tube, 0.0054g of 2-chloropropionic acid propinyl ester initiator, 0.0009g of cuprous chloride catalyst and 1330. mu.L of N, N-dimethylaminoethyl methacrylate were sequentially added to the ethanol solution, and finally 0.04mg of Me was added6Cyclam and 0.01mg of ATRP initiator (accounting for 1.5 percent of the total mass of the sample) are heated to 70 ℃ for reaction for 4 hours, after the reaction is finished, the product is taken out after being cooled to room temperature, is dissolved in THF, is purified by neutral alumina column chromatography, is subjected to rotary evaporation of solvent, and is dried in vacuum at the temperature of 40 ℃ to obtain colorless viscous solid.
(2) 0.002g of poly (N, N-dimethylaminoethyl methacrylate) was added into 10mL of ethanol solution and stirred magnetically for 30 min.
(3) Preparing a silver nanowire solution: 1g of polyvinylpyrrolidone (PVP) was added to 50 ml of Ethylene Glycol (EG) and dissolved by stirring. Then 3ml of 0.1 mol/l ferric chloride solution is added into the solution and stirred evenly. The mixed solution was put into a 100 ml reaction vessel, 12 ml of 0.12M silver nitrate solution was added dropwise to the mixed solution when the temperature reached 150 ℃, sufficiently stirred to be completely mixed, and then reacted at 170 ℃ for 5 hours. After the reaction is completed, the reaction solution is naturally cooled to room temperature, and then the reaction solution is transferred to a centrifuge tube and is centrifugally washed 5 times by using ethanol at the rotating speed of 3000 rpm. And pouring out supernatant liquid, adding the obtained silver nanowire precipitate into absolute ethyl alcohol, and performing ultrasonic dispersion to form a mixed solution of 5 mg/mL.
(4) Weighing 4mL of silver nanowire solution, adding the mixed solution, and ultrasonically stirring for 30min to uniformly disperse the silver nanowires in the mixed solution.
(5) Then 3g of PDMS was added and 0.1g of dichloromethane was added with constant stirring, and after placing in a rotor, magnetic stirring was carried out for 30 min.
(6) 0.3g of octamethylcyclotetrasiloxane curing agent (PDMS: curing agent = 10: 1) was weighed and added to the above mixture, and stirred for 40 min; and (5) placing the mixed solution into a vacuum furnace to remove bubbles for 30 min.
(7) Transferring the mixed solution to a coating substrate, and then coating the mixed solution by using a spin coater to form a film with the thickness of 1 mm; then putting the mixture into an oven to keep the constant temperature of 60 ℃ and heating the mixture for 3 hours. And then peeling the sensor to prepare a film, cutting the film into a size of 5cm multiplied by 5cm, and adhering copper foils to two sides of the film to obtain the flexible transparent temperature sensor.
In the prepared flexible transparent temperature sensor, the resistivity is respectively changed from the room temperature environment to 37.5 ℃, 38.0 ℃ and 39.0 ℃, the resistivity is-57%, -45% and-36%, and the corresponding time is about 24 seconds, so the flexible transparent temperature sensor has great advantages in clinical care. The large length-diameter ratio and the high specific surface area of the silver nanowires effectively increase the area of the conductive network and improve the temperature-sensitive performance of the sensor. The resistance change is not obvious within the range of minus 40-30 ℃, the linearity is 86.88%, but the thermal expansion phenomenon is generated along with the rise of the temperature, the conductive mesh area of the sensor is reduced due to the extrusion of the polymer material, and the resistance is reduced within the range of 30-60 ℃.
Example 2
(1) Preparation of poly (N, N-dimethylaminoethyl methacrylate): after evacuating and charging nitrogen gas 5 times in a polymerization tube, 0.0054g of 2-chloropropionic acid propinyl ester initiator, 0.0009g of cuprous chloride catalyst and 1330. mu.L of N, N-dimethylaminoethyl methacrylate were sequentially added to the ethanol solution, and finally 0.04mg of Me was added6Cyclam and 0.01mg ATRP initiator (accounting for 1.5 percent of the total mass of the sample), heating to 70 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, taking out the product, dissolving the product in THF, purifying by neutral alumina column chromatography, rotationally evaporating the solvent, and drying in vacuum at 40 ℃ to obtain colorless viscous solid
(2) 0.004g of poly (N, N-dimethylaminoethyl methacrylate) is added into 10mL of ethanol solution and stirred magnetically for 30 min.
(3) Preparing a silver nanowire solution: 1g of polyvinylpyrrolidone (PVP) was added to 50 ml of Ethylene Glycol (EG) and dissolved by stirring. Then, a certain amount of 3ml of 0.1 mol/l ferric chloride solution is added into the solution and stirred uniformly. The mixed solution was put into a 100 ml reaction vessel, 12 ml of 0.12M silver nitrate solution was added dropwise to the mixed solution when the temperature reached 150 ℃, sufficiently stirred to be completely mixed, and then reacted at 170 ℃ for 5 hours. After the reaction is completed, the reaction solution is naturally cooled to room temperature, and then the reaction solution is transferred to a centrifuge tube and is centrifugally washed 5 times by using ethanol at the rotating speed of 3000 rpm. And pouring out supernatant liquid, adding the obtained silver nanowire precipitate into absolute ethyl alcohol, and performing ultrasonic dispersion to form a mixed solution of 5 mg/mL.
(4) Weighing 4mL of silver nanowire solution, adding the mixed solution, and ultrasonically stirring for 30min to uniformly disperse the silver nanowires in the mixed solution.
(5) Then 3g of PDMS was added and 0.1g of dichloromethane was added with constant stirring, and after placing in a rotor, magnetic stirring was carried out for 30 min.
(6) 0.3g of octamethylcyclotetrasiloxane curing agent (PDMS: curing agent = 10: 1) was weighed and added to the above mixture, and stirred for 40 min; and (5) placing the mixed solution into a vacuum furnace to remove bubbles for 30 min.
(7) Transferring the mixed solution to a coating substrate, and then coating the mixed solution by using a spin coater to form a film with the thickness of 1 mm; then putting the mixture into an oven to keep the constant temperature of 60 ℃ and heating the mixture for 3 hours. And then peeling the sensor to prepare a film, cutting the film into a size of 5cm multiplied by 5cm, and adhering copper foils to two sides of the film to obtain the flexible transparent temperature sensor.
In the prepared flexible transparent temperature sensor, the resistivity is respectively changed from the room temperature environment to 37.5 ℃, 38.0 ℃ and 39.0 ℃, the resistivity is-66%, -49% and-42%, and the corresponding time is about 19 seconds, so the flexible transparent temperature sensor has great advantages in clinical care. The large length-diameter ratio and the high specific surface area of the silver nanowires effectively increase the area of the conductive network and improve the temperature-sensitive performance of the sensor. The resistance change is not obvious within the range of minus 40-30 ℃, the linearity is 86.88%, but the thermal expansion phenomenon is generated along with the rise of the temperature, the conductive mesh area of the sensor is reduced due to the extrusion of the polymer material, and the resistance is reduced within the range of 30-60 ℃.
Example 3
(1) Preparation of poly (N, N-dimethylaminoethyl methacrylate): after evacuating and charging nitrogen gas 5 times in a polymerization tube, 0.0054g of 2-chloropropionic acid propinyl ester initiator, 0.0009g of cuprous chloride catalyst and 1330. mu.L of N, N-dimethylaminoethyl methacrylate were sequentially added to the ethanol solution, and finally 0.04mg of Me was added6Cyclam and 0.01mg of ATRP initiator (accounting for 1.5 percent of the total mass of the sample), heating to 70 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, taking out the product, dissolving the product in THF, purifying by neutral alumina column chromatography, rotationally evaporating the solvent, and drying in vacuum at a certain temperature to obtain a colorless viscous solid
(2) 0.002g of poly (N, N-dimethylaminoethyl methacrylate) was added into 10mL of ethanol solution and stirred magnetically for 30 min.
(3) Preparing a silver nanowire solution: 1g of polyvinylpyrrolidone (PVP) was added to 50 ml of Ethylene Glycol (EG) and dissolved by stirring. Then 3ml of 0.1 mol/l ferric chloride solution is added into the solution and stirred evenly. The mixed solution was put into a 100 ml reaction vessel, 12 ml of 0.12M silver nitrate solution was added dropwise to the mixed solution when the temperature reached 150 ℃, sufficiently stirred to be completely mixed, and then reacted at 170 ℃ for 5 hours. After the reaction is completed, the reaction solution is naturally cooled to room temperature, and then the reaction solution is transferred to a centrifuge tube and is centrifugally washed 5 times by using ethanol at the rotating speed of 3000 rpm. And pouring out supernatant liquid, adding the obtained silver nanowire precipitate into absolute ethyl alcohol, and performing ultrasonic dispersion to form a mixed solution of 5 mg/mL.
(4) Weighing 0.4mL of silver nanowire solution, adding the mixed solution, and ultrasonically stirring for 30min to uniformly disperse the silver nanowires in the mixed solution.
(5) Then 3g of PDMS was added and 0.1g of dichloromethane was added with constant stirring, and after placing in a rotor, magnetic stirring was carried out for 30 min.
(6) 0.3g of octamethylcyclotetrasiloxane curing agent (PDMS: curing agent = 10: 1) was weighed and added to the above mixture, and stirred for 40 min; and (5) placing the mixed solution into a vacuum furnace to remove bubbles for 30 min.
(7) Transferring the mixed solution to a coating substrate, and then coating the mixed solution by using a spin coater to form a film with the thickness of 1 mm; then putting the mixture into an oven to keep the constant temperature of 60 ℃ and heating the mixture for 3 hours. And then peeling the sensor to prepare a film, cutting the film into a size of 5cm multiplied by 5cm, and adhering copper foils to two sides of the film to obtain the flexible transparent temperature sensor.
In the prepared flexible transparent temperature sensor, the resistivity is respectively changed from the room temperature environment to 37.5 ℃, 38.0 ℃ and 39.0 ℃, the resistivity is-52%, -41% and-32%, and the corresponding time is about 28 seconds, so the flexible transparent temperature sensor has great advantages in clinical care. The large length-diameter ratio and the high specific surface area of the silver nanowires effectively increase the area of the conductive network and improve the temperature-sensitive performance of the sensor. The resistance change is not obvious within the range of minus 40-30 ℃, the linearity is 86.88%, but the thermal expansion phenomenon is generated along with the rise of the temperature, the conductive mesh area of the sensor is reduced due to the extrusion of the polymer material, and the resistance is reduced within the range of 30-60 ℃.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a flexible transparent temperature sensor is characterized by comprising the following steps:
(1) preparation of poly (N, N-dimethylaminoethyl methacrylate): vacuumizing and filling nitrogen for several times in a polymerization tube, taking 2-chloropropionic acid propinyl ester as an initiator, and reacting cuprous chloride catalyst and N, N-dimethylaminoethyl methacrylate according to a mass ratio of 0.5-0.7: 0.1: 90-110 are added into the ethanol solution in sequence, and finally Me accounting for 1-2 percent of the total mass of the raw materials is added6Heating the Cyclam and an ATRP initiator for reaction, cooling to room temperature after the reaction is finished, taking out a product, dissolving the product in THF, purifying by neutral alumina column chromatography, rotationally evaporating a solvent, and drying in vacuum to obtain a colorless sticky solid, namely the poly (N, N-dimethylaminoethyl methacrylate);
(2) adding poly N, N-dimethylaminoethyl methacrylate into the ethanol solution, and stirring to obtain a poly N, N-dimethylaminoethyl methacrylate solution;
(3) preparing a silver nanowire solution: adding polyvinylpyrrolidone into ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, and then adding ferric chloride solution and stirring uniformly; and then transferring the obtained mixed solution into a reaction kettle, and dropwise adding a silver nitrate solution into the mixed solution when the temperature is raised to 145-155 ℃, wherein the mass ratio of ferric chloride to silver nitrate is 1: 4-6, fully stirring, then reacting at the temperature of 155-165 ℃ for 4-8 h, cooling to room temperature after the reaction is completed, then transferring the reaction liquid into a centrifuge tube, and performing centrifugal washing by using ethanol; finally, pouring out supernatant liquor, adding the obtained silver nanowire precipitate into absolute ethyl alcohol, and performing ultrasonic dispersion to form a silver nanowire solution;
(4) mixing the silver nanowire solution with the poly N, N-dimethylaminoethyl methacrylate solution, and ultrasonically stirring to obtain a mixed solution;
(5) then adding PDMS and dichloromethane into the mixed solution, and uniformly stirring;
(6) adding octamethylcyclotetrasiloxane curing agent accounting for 5-15% of the mass of PDMS, ultrasonically stirring, and placing the obtained mixed solution into a vacuum furnace to remove bubbles;
(7) transferring the mixed solution to a coating substrate, coating the mixed solution by using a spin coater to form a coating film, controlling the thickness of the film to be 1-2mm, and heating at constant temperature;
(8) and drying and curing the obtained coating, peeling off the coating from the coated substrate to prepare a film, and adhering copper foils on two sides of the film to obtain the flexible transparent temperature sensor.
2. The preparation method according to claim 1, wherein in the step (1), the polymerization tube is filled with nitrogen for 3-5 times, an ATRP initiator with an alkynyl group at the end is selected, the reaction temperature is 70-80 ℃, and the reaction time is 4-6 h.
3. The preparation method according to claim 1, wherein in the step (1), tetrahydrofuran is selected as an eluent for neutral alumina column chromatography, and the drying temperature is 40-60 ℃ in vacuum for 24-30 h.
4. The method according to claim 1, wherein in the step (2), the stirring time is 20 to 40min, and the concentration of the poly (N, N-dimethylaminoethyl methacrylate) solution is 15 to 30 wt%.
5. The method according to claim 1, wherein in the step (3), the mass ratio of polyvinylpyrrolidone to ethylene glycol is 2: 95-105; the centrifugal speed is 3000-; the concentration of the silver nanowire solution is 1-3 mg/ml.
6. The preparation method according to claim 1, wherein in the step (4), the mass ratio of the poly (N, N-dimethylaminoethyl methacrylate) to the silver nanowires is 1: 2-10.
7. The method according to claim 1, wherein in the step (5), the ratio of the total amount of the PDMS and the dichloromethane to the mixed solution is 8-12:1, the ratio of the amount of the PDMS to the dichloromethane is 100:2-4, and the stirring time is 30-50 min.
8. The method of claim 1, wherein in step (6), the ultrasonic agitation is performed for 40-60min, and the degassing time is 0.5-1 h.
9. The method as set forth in claim 1, wherein in the step (7), the spin speed of the spin coater is 400-600rpm, the heating temperature is 60-70 ℃, and the constant temperature heating time is 3-5 h.
10. The method according to claim 1, wherein in the step (8), the drying and curing temperature is 75 to 85 ℃ and the curing time is 4 to 6 hours.
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