CN112362189B - 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, which adopts PDMS as a substrate, silver nanowires as conductive filling materials, polymethacrylate(s) as temperature sensitive materials, and the PDMS has good transparency, chemical stability, excellent thermal expansibility, excellent conductivity and good flexibility. With polymethacrylates there is a low critical phase transition temperature (LCST), temperature sensitive property that the volume will be abrupt near LCST; 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 devices present a great development prospect. Based on the characteristics of light weight, good biocompatibility and the like of the flexible electronic sensor, the flexible electronic sensor is widely focused. Current research on flexible wearable sensors focuses on pressure, gas and humidity, with less related research on flexible temperature sensors. The temperature is an important index for measuring the physiological information and environmental conditions of human bodies, and is widely paid attention to.
The traditional flexible temperature sensor adopts polyethylene, high-density polyethylene and other olefins 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 process methods have high sensitivity and good stretchability, the flexible temperature sensors still have larger difference in performance compared with the traditional temperature sensors, and have high cost and complicated manufacturing process.
The silver nanowire keeps excellent flexibility and light transmittance of metallic silver, and the elastic conductor manufactured by the silver nanowire has the characteristics of simple manufacturing process, expandability, excellent conductive performance, good transparency and high corrosion resistance.
PDMS is a high molecular organosilicon compound, which has high chemical stability, good insulativity, excellent adhesion, low material cost, simple manufacture and use, good light transmittance and good biocompatibility, and can be widely used in the field of microelectronics. The solid PDMS is nontoxic, nonflammable, good in light transmittance and high in flexibility.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a flexible transparent temperature sensor, which adopts PDMS as a substrate, silver nanowires as conductive filling materials, polymethacrylate(s) as temperature sensitive materials, and the PDMS has good transparency, chemical stability and excellent thermal expansibility, and the silver nanowires have excellent conductivity and good flexibility. With polymethacrylates there is a low critical phase transition temperature (LCST), temperature sensitive property that the volume will be abrupt near LCST; 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): after vacuumizing and filling nitrogen in a polymerization tube for several times, taking 2-chloropropionic acid propyne ester as an initiator, and taking a cuprous chloride catalyst and methacrylic acid N, N-dimethylaminoethyl ester according to the mass ratio of 0.5-0.7:0.1: sequentially adding 90-110 into ethanol solution, and adding Me accounting for 1-2% of the total mass of the raw materials 6 Cyclam and ATRPInitiator (Me) 6 The mass ratio of the Cyclam to the ATRP initiator is 1: 2) And heating to react, cooling to room temperature after the reaction is completed, 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 colorless viscous solid, namely the N, N-dimethylaminoethyl polymethacrylate.
The activity of the polymerization process is controllable, and the polymer with low dispersity and definite molecular weight and molecular structure can be synthesized.
(2) Adding the N, N-dimethylaminoethyl polymethacrylate into an ethanol solution, and stirring to obtain the N, N-dimethylaminoethyl polymethacrylate solution.
(3) Preparation of silver nanowire solution: adding polyvinylpyrrolidone into ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding ferric chloride solution, and stirring uniformly; 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 at 155-165 ℃ for 4-8 h, cooling to room temperature after the reaction is completed, transferring the reaction solution into a centrifuge tube, and centrifugally 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 N, N-dimethylaminoethyl polymethacrylate solution, and stirring by ultrasonic to obtain a mixed solution.
(5) And then adding PDMS and methylene dichloride into the mixed solution, and stirring uniformly.
Preventing the solution from forming colloid in advance in the stirring process to influence the dispersibility of the material, and adding methylene dichloride to keep the fluidity of the solution. The methylene chloride was completely volatilized during stirring.
(6) Adding octamethyl cyclotetrasiloxane curing agent with the mass of PDMS of 5-15%, stirring by ultrasonic, and putting the obtained mixed solution into a vacuum furnace to remove bubbles.
The thickness of the PDMS film is different, so that the tensile property of the film is influenced, and further the surface characteristics of the conductive composite material, the flexibility and the conductive stability of the conductive film are also influenced. Therefore, the thickness of the film needs to be controlled to be 1-2mm, and the requirement of the prepared film on the uniformity of the film thickness is high, so that a spin coater is selected for spin coating.
(7) Transferring the mixed solution to a coating substrate, coating the mixed solution to form a coating film by using a spin coater, controlling the thickness of the film to be 1-2mm, and heating at constant temperature;
(8) And drying and solidifying the obtained coating film, then stripping the coating film from the coating film 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), nitrogen is filled into a polymerization tube for 3-5 times, an ATRP initiator with an alkynyl at the tail end is selected, the reaction temperature is 70-80 ℃, and the reaction time is 4-6 hours.
Preferably, in the step (1), tetrahydrofuran is selected as an eluent for neutral alumina column chromatography, and the vacuum drying temperature is 40-60 ℃ and the time is 24-30h.
Preferably, in the step (2), the stirring time is 20-40min, and the concentration of the N, N-dimethylaminoethyl polymethacrylate solution is 15-30wt%.
Preferably, in the step (3), the mass ratio of polyvinylpyrrolidone to ethylene glycol is 2:95-105; the centrifugal rotating speed is 3000-5000rpm, and washing is carried out for 5-7 times; the concentration of the silver nanowire solution is 1-3 mg/ml.
Preferably, in the step (4), the mass ratio of the N, N-dimethylaminoethyl polymethacrylate to the silver nanowire 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 and the dichloromethane is 100:2-4, and the stirring time is 30-50min.
Preferably, in the step (6), the ultrasonic stirring time is 40-60min, and the degassing time is 0.5-1h.
Preferably, in the step (7), the spin coating speed of the spin coater is 400-600rpm, the heating temperature is 60-70 ℃, and the constant temperature heating time is 3-5h.
Preferably, in the step (8), the drying and curing temperature is 75-85 ℃ and the curing time is 4-6h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention uses the electrochemical sensitivity of silver nanometer wire and the temperature sensitivity of polymethyl methacrylate N, N-dimethyl amino ethyl ester, and the product responds sensitively to external force.
(2) The invention adopts the polymethyl methacrylate N, N-dimethyl amino ethyl ester as a temperature sensitive material, and the product has good transparency.
(3) The invention adopts the polymethyl methacrylate N, N-dimethyl amino ethyl ester and PDMS, thereby ensuring that the product has good biocompatibility.
Detailed Description
The invention is further described below with reference to examples.
Example 1
(1) Preparation of poly (N, N-dimethylaminoethyl methacrylate): after 5 times of vacuum filling nitrogen in the polymerization tube, 0.0054g of 2-chloropropionate propynyl ester initiator, 0.0009g of cuprous chloride catalyst and 1330 mu L of N, N-dimethylaminoethyl methacrylate are added to the ethanol solution in sequence, and finally 0.04mg of Me is added 6 Cyclam and 0.01mg of ATRP initiator (accounting for 1.5% of the total mass of the sample) are heated to 70 ℃ for 4 hours, the reaction is completed, the reaction is cooled to room temperature, the product is taken out, dissolved in THF, purified by neutral alumina column chromatography, the solvent is rotationally evaporated, and the colorless viscous solid is obtained by vacuum drying at the temperature of 40 ℃.
(2) 0.002g of N, N-dimethylaminoethyl polymethacrylate was added to 10mL of ethanol solution and magnetically stirred for 30min.
(3) Preparation of silver nanowire solution: 1g polyvinylpyrrolidone (PVP) was added to 50 ml Ethylene Glycol (EG) and dissolved with stirring. Then 3ml of 0.1 mol/l ferric chloride solution was added to the solution and stirred well. The mixed solution was placed in a reaction kettle of 100 ml, and when the temperature reached 150 ℃, 0.12M silver nitrate solution of 12 ml was added dropwise to the mixed solution, and the mixture was thoroughly mixed with stirring, followed by reaction at 170 ℃ for 5h. After the reaction was completed, naturally cooled to room temperature, and then the reaction solution was transferred to a centrifuge tube, and subjected to centrifugal washing 5 times with ethanol at a rotation speed of 3000 rpm. The supernatant was decanted and the resulting silver nanowire precipitate was added to absolute ethanol and sonicated to form a 5mg/mL mixed solution.
(4) Weighing 4mL of silver nanowire solution, adding the mixed solution, and stirring for 30min by ultrasonic to uniformly disperse the silver nanowires in the mixed solution.
(5) Then 3g of PDMS was added and 0.1g of dichloromethane was added, stirring was continued, and after putting into the rotor magnetic stirring for 30min.
(6) 0.3g of octamethyl cyclotetrasiloxane curing agent (PDMS: curing agent=10:1) is weighed and added into the mixed solution, and the mixed solution is stirred for 40min; and (5) placing the mixed solution into a vacuum furnace to remove bubbles for 30min.
(7) Transferring the mixed solution onto a coating substrate, and coating the mixed solution with a spin coater for molding, wherein the thickness of the coating is 1mm; then put into an oven to be heated for 3 hours at the constant temperature of 60 ℃. And then stripping the sensor to prepare a film, cutting the film into a size of 5cm multiplied by 5cm, and adhering copper foils on two sides of the film to obtain the flexible transparent temperature sensor.
In the manufactured flexible transparent temperature sensor, the temperature is changed from room temperature environment to 37.5 ℃, 38.0 ℃ and 39.0 ℃, the resistivity is respectively-57%, -45% and-36%, and the corresponding time is about 24 seconds, so that the 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 sensitivity of the sensor. The resistance change is not obvious within the range of-40-30 ℃, the linearity is 86.88%, but the thermal expansion phenomenon occurs along with the temperature rise, the area of the conductive network 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 5 times of vacuum filling nitrogen in the polymerization tube, 0.0054g of 2-chloropropionate propynyl ester initiator, 0.0009g of cuprous chloride catalyst and 1330 mu L of N, N-dimethylaminoethyl methacrylate are added to the ethanol solution in sequence, and finally 0.04mg of Me is added 6 Cyclam and 0.01mg of ATRP initiator(1.5% of the total mass of the sample), heating to 70 ℃ for 4 hours, cooling to room temperature after the reaction is completed, taking out the product, dissolving the product in THF, purifying by neutral alumina column chromatography, rotary evaporating the solvent, and vacuum drying at 40 ℃ to obtain colorless viscous solid
(2) 0.004g of N, N-dimethylaminoethyl polymethacrylate was added to 10mL of ethanol solution and magnetically stirred for 30min.
(3) Preparation of silver nanowire solution: 1g polyvinylpyrrolidone (PVP) was added to 50 ml Ethylene Glycol (EG) and dissolved with stirring. Then, a certain amount of 3ml of 0.1 mol/l ferric chloride solution was added to the solution and stirred well. The mixed solution was placed in a reaction kettle of 100 ml, and when the temperature reached 150 ℃, 0.12M silver nitrate solution of 12 ml was added dropwise to the mixed solution, and the mixture was thoroughly mixed with stirring, followed by reaction at 170 ℃ for 5h. After the reaction was completed, naturally cooled to room temperature, and then the reaction solution was transferred to a centrifuge tube, and subjected to centrifugal washing 5 times with ethanol at a rotation speed of 3000 rpm. The supernatant was decanted and the resulting silver nanowire precipitate was added to absolute ethanol and sonicated to form a 5mg/mL mixed solution.
(4) Weighing 4mL of silver nanowire solution, adding the mixed solution, and stirring for 30min by ultrasonic to uniformly disperse the silver nanowires in the mixed solution.
(5) Then 3g of PDMS was added and 0.1g of dichloromethane was added, stirring was continued, and after putting into the rotor magnetic stirring was performed for 30min.
(6) 0.3g of octamethyl cyclotetrasiloxane curing agent (PDMS: curing agent=10:1) is weighed and added into the mixed solution, and the mixed solution is stirred for 40min; and (5) placing the mixed solution into a vacuum furnace to remove bubbles for 30min.
(7) Transferring the mixed solution onto a coating substrate, and coating the mixed solution with a spin coater for molding, wherein the thickness of the coating is 1mm; then put into an oven to be heated for 3 hours at the constant temperature of 60 ℃. And then stripping the sensor to prepare a film, cutting the film into a size of 5cm multiplied by 5cm, and adhering copper foils on two sides of the film to obtain the flexible transparent temperature sensor.
In the manufactured flexible transparent temperature sensor, the temperature is changed from room temperature environment to 37.5 ℃, 38.0 ℃ and 39.0 ℃, the resistivity is respectively-66%, -49% and-42%, and the corresponding time is about 19 seconds, so that the 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 sensitivity of the sensor. The resistance change is not obvious within the range of-40-30 ℃, the linearity is 86.88%, but the thermal expansion phenomenon occurs along with the temperature rise, the area of the conductive network 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 5 times of vacuum filling nitrogen in the polymerization tube, 0.0054g of 2-chloropropionate propynyl ester initiator, 0.0009g of cuprous chloride catalyst and 1330 mu L of N, N-dimethylaminoethyl methacrylate are added to the ethanol solution in sequence, and finally 0.04mg of Me is added 6 Cyclam and 0.01mg of ATRP initiator (accounting for 1.5% of the total mass of the sample) are heated to 70 ℃ for 4 hours, the reaction is completed, the reaction is cooled to room temperature, the product is taken out and dissolved in THF, neutral alumina column chromatography purification is carried out, the solvent is rotationally evaporated, and vacuum drying is carried out under a certain temperature condition, thus obtaining colorless viscous solid
(2) 0.002g of N, N-dimethylaminoethyl polymethacrylate was added to 10mL of ethanol solution and magnetically stirred for 30min.
(3) Preparation of silver nanowire solution: 1g polyvinylpyrrolidone (PVP) was added to 50 ml Ethylene Glycol (EG) and dissolved with stirring. Then 3ml of 0.1 mol/l ferric chloride solution was added to the solution and stirred well. The mixed solution was placed in a reaction kettle of 100 ml, and when the temperature reached 150 ℃, 0.12M silver nitrate solution of 12 ml was added dropwise to the mixed solution, and the mixture was thoroughly mixed with stirring, followed by reaction at 170 ℃ for 5h. After the reaction was completed, naturally cooled to room temperature, and then the reaction solution was transferred to a centrifuge tube, and subjected to centrifugal washing 5 times with ethanol at a rotation speed of 3000 rpm. The supernatant was decanted and the resulting silver nanowire precipitate was added to absolute ethanol and sonicated to form a 5mg/mL mixed solution.
(4) 0.4mL of silver nanowire solution is weighed, the mixed solution is added, and ultrasonic stirring is carried out for 30min, so that silver nanowires are uniformly dispersed in the mixed solution.
(5) Then 3g of PDMS was added and 0.1g of dichloromethane was added, stirring was continued, and after putting into the rotor magnetic stirring for 30min.
(6) 0.3g of octamethyl cyclotetrasiloxane curing agent (PDMS: curing agent=10:1) is weighed and added into the mixed solution, and the mixed solution is stirred for 40min; and (5) placing the mixed solution into a vacuum furnace to remove bubbles for 30min.
(7) Transferring the mixed solution onto a coating substrate, and coating the mixed solution with a spin coater for molding, wherein the thickness of the coating is 1mm; then put into an oven to be heated for 3 hours at the constant temperature of 60 ℃. And then stripping the sensor to prepare a film, cutting the film into a size of 5cm multiplied by 5cm, and adhering copper foils on two sides of the film to obtain the flexible transparent temperature sensor.
In the manufactured flexible transparent temperature sensor, the temperature is changed from room temperature environment to 37.5 ℃, 38.0 ℃ and 39.0 ℃, the resistivity is respectively-52%, -41% and-32%, and the corresponding time is about 28 seconds, so that the 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 sensitivity of the sensor. The resistance change is not obvious within the range of-40-30 ℃, the linearity is 86.88%, but the thermal expansion phenomenon occurs along with the temperature rise, the area of the conductive network 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 unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the flexible transparent temperature sensor is characterized by comprising the following steps of:
(1) Preparation of poly (N, N-dimethylaminoethyl methacrylate): vacuumizing and filling nitrogen in a polymerization tube for several times, sequentially adding a cuprous chloride catalyst and N, N-dimethylaminoethyl methacrylate serving as an initiator into an ethanol solution according to the mass ratio of 0.5-0.7:0.1:90-110, and finally adding Me accounting for 1-2% of the total mass of the raw materials 6 The preparation method comprises the steps of (1) heating a Cyclam and an ATRP initiator to react, cooling to room temperature after the reaction is completed, 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 colorless viscous solid, namely N, N-dimethylaminoethyl polymethacrylate;
(2) Adding the N, N-dimethylaminoethyl polymethacrylate into an ethanol solution, and stirring to obtain a N, N-dimethylaminoethyl polymethacrylate solution;
(3) Preparation of silver nanowire solution: adding polyvinylpyrrolidone into ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding ferric chloride solution, and stirring uniformly; transferring the obtained mixed solution into a reaction kettle, and dripping 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 155-165 ℃ for 4-8 h, cooling to room temperature after the reaction is completed, transferring the reaction liquid into a centrifuge tube, and centrifugally washing by using ethanol; 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; the mass ratio of polyvinylpyrrolidone to glycol is 2:95-105; the concentration of the silver nanowire solution is 1-3 mg/ml;
(4) Mixing a silver nanowire solution with a polymethyl methacrylate N, N-dimethylaminoethyl ester solution, and carrying out ultrasonic stirring to obtain a mixed solution; the mass ratio of the polymethyl methacrylate to the N, N-dimethyl amino ethyl ester to the silver nanowire is 1:2-10;
(5) Then adding PDMS and methylene dichloride into the mixed solution, and uniformly stirring; the dosage ratio of the total amount of PDMS and dichloromethane to the mixed solution is 8-12:1, and the dosage ratio of PDMS to dichloromethane is 100:2-4;
(6) Adding octamethyl cyclotetrasiloxane curing agent with the mass of PDMS of 5-15%, stirring by ultrasonic, and putting the obtained mixed solution into a vacuum furnace to remove bubbles;
(7) Transferring the mixed solution to a coating substrate, coating the mixed solution to form a coating film by using a spin coater, controlling the thickness of the film to be 1-2mm, and heating at constant temperature;
(8) And drying and solidifying the obtained coating film, then stripping the coating film from the coating film 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), nitrogen is filled into the polymerization tube for 3-5 times, an ATRP initiator with alkynyl at the tail end is selected, and the reaction temperature is 70-80 ℃ and the reaction time is 4-6 hours.
3. The method according to claim 1, wherein in the step (1), tetrahydrofuran is used as an eluent for neutral alumina column chromatography, and the vacuum drying temperature is 40-60 ℃ for 24-30h.
4. The process according to claim 1, wherein in the step (2), the stirring time is 20 to 40 minutes and the concentration of the solution of N, N-dimethylaminoethyl methacrylate is 15 to 30% by weight.
5. The method according to claim 1, wherein in the step (3), the centrifugal speed is 3000 to 5000rpm and the washing is performed 5 to 7 times.
6. The process according to claim 1, wherein in step (5), the stirring time is 30 to 50 minutes.
7. The process according to claim 1, wherein in step (6), the ultrasonic agitation is carried out for 40 to 60 minutes and the degassing time is 0.5 to 1 hour.
8. The method according to claim 1, wherein in the step (7), the spin coating speed of the spin coater is 400 to 600rpm, the heating temperature is 60 to 70℃and the constant temperature heating time is 3 to 5 hours.
9. The process according to claim 1, wherein in step (8), the drying and curing temperature is 75 to 85℃and the curing time is 4 to 6 hours.
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