CN110702746B - Condensed ring squaramide polymer, humidity-sensitive sensor based on condensed ring squaramide polymer and preparation method of humidity-sensitive sensor - Google Patents
Condensed ring squaramide polymer, humidity-sensitive sensor based on condensed ring squaramide polymer and preparation method of humidity-sensitive sensor Download PDFInfo
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- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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Abstract
The invention discloses a condensed ring squaramide polymer, a humidity-sensitive sensor based on the condensed ring squaramide polymer and a preparation method of the humidity-sensitive sensor. The humidity sensor of the present invention has the following advantages: the preparation is convenient and fast, and the operation is simple; the response time is short and is less than 2 seconds; the recovery time is short and is less than 1 second; the device performance is stable; under high humidity environment, the device humidity hysteresis is small, 6%.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to two humidity-sensitive sensors based on condensed ring squaramide polymers, a preparation method of the humidity-sensitive sensors and application of the humidity-sensitive sensors in air humidity detection.
Background
With the development of science and technology, the requirement for the environmental humidity is more severe in many fields, such as aerospace industry, agriculture, precision machinery and laboratories, which need to effectively monitor the environmental humidity. The core of the humidity sensor is a humidity-sensitive device, which directly adsorbs water molecules by utilizing the adsorption effect of a humidity-sensitive material, so that the humidity-sensitive characteristic quantities such as surface conductance, volume, dielectric constant and the like of the humidity-sensitive device are changed, and an electrical signal is output through the detection and conversion of a change circuit so as to detect the humidity. The currently known moisture sensitive materials mainly include electrolytes, ceramic-based materials, porous metal oxides and high molecular polymers. Wherein, the electrolyte salt in the electrolyte material is easy to absorb water and diluted, even flows out, and the moisture-sensing performance of the material is damaged; although ceramic and porous metal materials have excellent heat resistance and rapid response to humidity, the ceramic and porous metal materials have high temperature coefficient of resistance, poor reproducibility and interchangeability and are not pollution-resistant. The high molecular polymer humidity sensitive material gets more and more attention due to the excellent performances of rich material source, wide relative humidity range, small humidity hysteresis, high response speed and the like. In order to meet the requirements of the current market on the aspects of low price, practicability, easy preparation and the like of the sensor, a novel humidity-sensitive sensor needs to be developed urgently.
Disclosure of Invention
In view of the above situation, the present invention employs condensed ring square amide polymer 1, 5-PDS to prepare humidity-sensitive sensors, and detects air of different humidity by observing the complex impedance change of the sensors under different humidity. The invention tests the impedance change of the humidity-sensitive sensor under different frequencies, thereby selecting the maximum complex impedance of the humidity-sensitive sensor under 100 Hz. The invention also tests the adsorption and desorption performance of the device, and tests that the device has excellent adsorption and desorption capacity in the humidity atmosphere of 11-95%.
Wherein n is 40-50.
Specifically, the invention adopts the following technical scheme:
a fused ring squaramide polymer of the formula:
wherein n is 40-50.
The preparation method of the condensed ring squaramide polymer comprises the following steps of reacting 1, 5-diaminoanthraquinone and squaric acid in a solvent to obtain the condensed ring squaramide polymer.
In the technical scheme, the solvent is alcohol; the reaction is carried out for 15-20 h at 120-140 ℃, and the reaction is carried out for 18 h at 130 ℃ preferably.
The invention also discloses a preparation method of the squaramide polymer 1,5-PDAS, which comprises the following steps: dissolving 1, 5-diaminoanthraquinone and squaric acid in n-butyl alcohol, and heating for reaction; after the reaction is finished, cooling to room temperature, filtering the product, washing with tetrahydrofuran and acetone, and drying to obtain the squaramide polymer 1, 5-PDAS.
The invention discloses an application of the condensed ring squaramide polymer in preparing a humidity-sensitive sensor.
The invention discloses a humidity-sensitive device for a humidity-sensitive sensor, which consists of an interdigital electrode and a coating material covering the surface of the interdigital electrode, wherein the coating material is the condensed ring square amide polymer.
The invention discloses a humidity-sensitive sensor based on condensed ring squaramide polymer, which comprises an interdigital electrode and a coating material covered on the surface of the interdigital electrode, wherein the coating material is the condensed ring squaramide polymer. Further, the condensed ring squaramide polymer-based humidity sensor further comprises a substrate; the interdigital electrode consists of an alumina substrate and a silver-palladium alloy; the width of an interdigital of the interdigital electrode is 200-300 mu m, and the distance between the interdigital electrodes is 100-200 mu m; the thickness of the coating material is 100-400 mu m; the interdigital electrode takes alumina as a substrate, the thickness of the interdigital electrode is 1-2 mm, and the interdigital electrode is made of alumina (Al)2O3) A silver-palladium (Ag-Pd) alloy is disposed on the substrate, and the thickness is 100-200 nm.
The preparation method of the humidity-sensitive sensor based on the condensed ring squaramide polymer comprises the following steps: fixing the interdigital electrode on the substrate; and then brushing the solution of the condensed ring squaramide polymer on an interdigital electrode to obtain the humidity-sensitive sensor based on the condensed ring squaramide polymer. The preparation method of the moisture-sensitive sensor based on the squaramide polymer specifically comprises the following steps:
1) cleaning a substrate, and fixing interdigital electrodes on the substrate;
2) dissolving the squaramide polymer in a solvent according to the weight ratio of the squaramide polymer to the solvent =4: 1000-2000, and uniformly dispersing the squaramide polymer by ultrasonic waves to obtain a squaramide polymer solution;
3) and (3) brushing the squaramide polymer solution on the interdigital electrode, standing at room temperature, volatilizing the solvent, and drying at 60-80 ℃ for 1-2 hours to obtain the moisture-sensitive sensor based on the squaramide polymer.
Preferably, in the above production method, the substrate in step 1) is selected from any one of a glass substrate, a PE substrate, and an iron sheet substrate, and is preferably a glass substrate.
Preferably, in the above preparation method, the fixing in step 1) is performed by means of double-sided adhesive bonding.
Preferably, in the above preparation method, the solvent in step 2) is selected from any one of ethanol, dichloromethane and ethyl acetate, preferably ethanol.
Preferably, in the above preparation method, the brushing in step 3) is performed by a brush pen.
Preferably, in the above preparation method, the brushing manner in step 3) is as follows: and (4) brushing for multiple times, wherein after each brushing is finished, brushing is carried out again after the surface is dried.
Preferably, in the above preparation method, the drying in step 3) is performed by a vacuum oven;
preferably, in the above preparation method, the temperature of the drying in the step 3) is 60 ℃ for 1 hour.
The invention also discloses the application of the moisture-sensitive sensor based on the squaramide polymer in air humidity detection.
Compared with the prior art, the invention using the technical scheme has the following advantages:
(1) the device disclosed by the invention is convenient to prepare and simple to operate;
(2) the response time disclosed by the invention is short, and the response to humidity change is higher than that of common metal oxide;
(3) the invention has short recovery time and stable device performance;
(4) the device disclosed by the invention has strong moisture retention property under a high-humidity environment.
Drawings
FIG. 1 is a physical representation of a squaraine polymer-based moisture-sensitive sensor.
FIG. 2 shows the IR spectrum of 1, 5-PDS, a squaramide polymer.
FIG. 3 is a graph showing the effect of the humidity response test of the humidity-sensitive sensor based on the squaraine polymer 1, 5-PDS at different frequencies.
FIG. 4 is a graph showing adsorption and desorption curves of a humidity-sensitive sensor based on squaramide polymer 1,5-PDAS under different humidity conditions.
FIG. 5 is a graph of the effect of a recovery test of a moisture sensitive sensor based on squaramide polymer 1,5-PDAS at a relative humidity between 11% and 95%.
FIG. 6 is a graph of the effect of response time of a moisture sensitive sensor based on squaramide polymer 1, 5-PDS at relative humidity between 11% and 95%.
FIG. 7 is a graph of the effect of recovery time of a moisture sensitive sensor based on squaramide polymer 1,5-PDAS at relative humidities between 11% and 95%.
Detailed Description
The technical solutions of the present invention will be further described with reference to the accompanying drawings and specific embodiments. Unless otherwise indicated, reagents, materials, instruments and the like used in the following examples are commercially available. A schematic representation of a moisture-sensitive sensor based on squaramide polymers according to the invention is shown in FIG. 1.
Example 1: synthesis of Polymer 1,5-PDAS and preparation of sensor
(1) Synthesis of Polymer 1, 5-PDAS:
weighing 1, 5-diaminoanthraquinone (238.25 mg, 2 mmol) and squaric acid (114.06 mg, 2 mmol), placing in n-butanol (50 mL), heating at 130 ℃, refluxing for 18 h, cooling to room temperature after the reaction is finished, filtering the product, washing with tetrahydrofuran and acetone, and drying to obtain the squaramide polymer 1, 5-PDAS. The IR spectrum of 1,5-PDAS is shown in FIG. 2, and the molecular weight is 12000-16000.
As can be seen from fig. 2, after the polymerization reaction is completed, the characteristic peak of hydroxyl group in the squaric acid disappears, the characteristic peak of C = O double bond remains, and the peak position of the characteristic peak of C — N bond shifts to some extent due to the change of charge density, indicating that the polymer 1,5-PDAS has been successfully prepared.
(2) Preparing a sensor:
(a) cleaning the glass substrate, and bonding the interdigital electrode on the substrate by double-sided adhesive tape, wherein the interdigital electrode is made of Al2O3(1 mm) is a substrate on which an Ag-Pd alloy electrode (100 nm) is arranged and an interdigitalThe width is 0.2 μm, and the inter-digital distance is 0.2 μm;
(b) dissolving the 1,5-PDAS (4 mg) in ethanol (2 g), and performing ultrasonic treatment to uniformly disperse the solution to obtain an ethanol solution of a squaramide polymer;
(c) and (3) brushing the ethanol solution of the squaramide polymer on the interdigital electrode for 10 times, placing at room temperature, volatilizing ethanol, and placing in a vacuum oven to dry at 60 ℃ for 1 h to obtain the moisture-sensitive sensor based on the squaramide polymer, wherein the coating thickness is 300 mu m.
The interdigital electrode and the coating material covering the surface of the interdigital electrode form a humidity-sensitive device for the humidity-sensitive sensor.
Example 2: humidity-sensitive sensor impedance response measurement experiment for humidity under different frequencies
The device prepared in example 1 was placed in a test machine, the frequency was adjusted in the range of 10 Hz to 100 kHz, and the impedance change of the device in an atmosphere of different relative humidity, such as 11%, 33%, 54%, 75%, 85%, 95% was tested, and the results are shown in fig. 3.
As can be seen from FIG. 3, the humidity sensor based on the squaraine polymer 1, 5-PDS has different impedance changes under different frequency conditions for different concentrations of humidity atmosphere, and it can be seen that the response intensity of the device is strongest at 100 Hz.
Example 3: test for determining the recovery Performance of moisture-sensitive Sensors at relative humidities between 11% and 95%
Under the condition of the frequency of 100 Hz, the device was first placed under the relative humidity condition of 11% to stabilize the impedance, then placed under the relative humidity condition of 95%, and after the impedance was stabilized, the device was again placed under the relative humidity condition of 11% to repeat the above cycle, and the result is shown in FIG. 4.
For the moisture-sensitive sensor based on squaramide polymer 1, 5-PDS, it can be seen from FIG. 4 that the stability of the device is very good; as can be seen from fig. 5, the device test response time is as short as less than 2 s; it can be seen from fig. 6 that the recovery time of the device is as short as less than 1 s. Therefore, the device has the advantages of good stability, short response time and short recovery time.
Example 4: absorption and desorption performance determination experiment of humidity-sensitive sensor based on squaramide polymer
The control frequency is 100 Hz, the humidity-sensitive sensor is placed in different relative humidity atmospheres, the absorption and desorption performances of the device are tested, the result is shown in figure 7, and it can be seen that the absorption and desorption performances of the device are good, and the maximum humidity hysteresis is 6%.
Comparative example
The moisture sensor based on the squaramide polymer PEAB was prepared by replacing 1,5-PDAS of example 1 with PEAB and leaving the remainder unchanged, and the absorption and desorption properties of the device were measured by the test method of example 4, and the result showed that the maximum humidity hysteresis of the moisture sensor based on the squaramide polymer PEAB was 32%. It is shown that the structural composition of the aramid polymer has a great influence on its properties.
The chemical structural formula (n is 20-50) of PEAB is as follows:
in conclusion, the invention realizes the detection of air with different humidity by manufacturing the squaramide polymer into the resistance type film sensor with simple structure, has quick response and time, and has high application value for the control of the future environmental humidity.
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