CN114672020B - Preparation method of benzoxazinyl conjugated trapezoid polymer and application of benzoxazinyl conjugated trapezoid polymer in hydrogen sulfide detection - Google Patents
Preparation method of benzoxazinyl conjugated trapezoid polymer and application of benzoxazinyl conjugated trapezoid polymer in hydrogen sulfide detection Download PDFInfo
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Abstract
A preparation method of benzoxazinyl conjugated trapezoid polymer and application thereof in hydrogen sulfide detection. The benzoxazine conjugated trapezoidal polymer takes diamino benzenediol molecules as a monomer A, benzoquinone compounds as a monomer B, and the benzoxazine conjugated trapezoidal polymer passes through a polymerization reaction kettle and a vacuum atmosphere furnace to generate the benzoxazine trapezoidal conductive polymer, and then a gas sensor is prepared for detecting acid gases such as hydrogen sulfide. The invention has the advantages of simple preparation, low cost, high specificity and high sensitivity of hydrogen sulfide detection. The benzoxazine-based conjugated trapezoid polymer has remarkable semiconductor characteristics, can work at room temperature, has low power consumption requirements, is possibly suitable for a wearable sensor or on-site rapid detection of acute toxic and corrosive hydrogen sulfide gas, such as pipeline and sewage treatment, and can be used as a core material of a portable hydrogen sulfide tester, thereby having wide application prospects in the field of gas detection.
Description
Technical Field
The invention belongs to the technical field of high molecular semiconductors, and particularly relates to a preparation method of a benzoxazine conjugated trapezoid polymer and application of the benzoxazine conjugated trapezoid polymer in hydrogen sulfide detection.
Background
Hydrogen sulfide is a highly corrosive contaminant gas that is commonly found in natural gas streams and can also be produced by anaerobic bacterial decomposition of organics. According to the regulations of national institute of occupational safety and health, the allowable limit of contact of hydrogen sulfide with human body is about 20ppm, and more than 100ppm has direct danger to life, and the hydrogen sulfide has acute toxicity, which promotes development of low-cost and portable sensing technology, which can rapidly identify trace concentration of hydrogen sulfide in environments such as mines, natural gas pipelines, sewage treatment plants and the like. Thus, there has been considerable research interest in detecting exogenous hydrogen sulfide, and research into hydrogen sulfide sensors has been rapidly advancing. See: (1) Mzdek, luo SXL, kuK H, et al A chemiresistive methane sensor [ J ]. Proceedings of the National Academy of Sciences,2021,118 (2): e2022515118. The on-site hydrogen sulfide detection method mainly comprises two types: firstly, directly sampling and sending the sample into a laboratory, and carrying out energy spectrum analysis by adopting a gas chromatograph to obtain the concentration of the hydrogen sulfide, wherein the method has high accuracy, but belongs to single-point testing, and has the advantages of large sampling and sample measuring workload, long period and relatively high cost, so that the instantaneous change rule of the hydrogen sulfide is difficult to reflect in time; secondly, the hydrogen sulfide on-line detection equipment is arranged to detect the dynamic change of the concentration of the hydrogen sulfide in real time, and the method has high accuracy but high cost, and is suitable for sulfur-containing gas fields with concentrated distribution and relatively high concentration of the hydrogen sulfide gas well. At present, a portable hydrogen sulfide tester is adopted for detecting low-concentration hydrogen sulfide in an open-air real-time multipoint detection mode at a wellhead or a gas collecting station, and the method is convenient to operate and low in cost. Most of the core materials of the current portable hydrogen sulfide testers are inorganic materials, and the preparation process of the materials is relatively complex and has high requirements on manufacturing equipment. The high polymer material is simple to prepare, has lower requirements on manufacturing equipment and has lower cost, so that research on the hydrogen sulfide response high polymer of the core material of the portable hydrogen sulfide tester is completed.
According to the search literature, a trapezoidal polybenzoxazine polymer is synthesized by 1, 4-p-phenylenediamine and tetrachlorobenzoquinone at university of southeast in 2016, but the performance of the trapezoidal polybenzoxazine polymer as a supercapacitor material is mainly studied, the hydrogen sulfide detection performance is not mentioned, and the preparation method in the patent is different from the Xiaohui preparation method and different in application. See: (2) Gong X, zhang Y, wen H, et al Phenoxazine-Based Conjugated Ladder Polymers as Novel Electrode Materials for Supercapacitors [ J ]. ChemElectrochem,2016,3 (11): 1837-1846 (3) Xiaohui. Design of triphendioxazine-based photovoltaic materials, synthesis and Performance research [ D ]. University southeast, 2016.
Disclosure of Invention
The invention aims at solving the technical analysis and problems and provides a preparation method of a benzoxazine-based conjugated trapezoid polymer and application of the benzoxazine-based conjugated trapezoid polymer in hydrogen sulfide detection.
The technical scheme of the invention is as follows:
a process for preparing the benzoxazine-based conjugated trapezoidal polymer includes such steps as polymerizing the diaminobenzenediol as monomer A, benzoquinone as monomer B, and heat treating in vacuum furnace to obtain ring,
wherein the R group is a chlorine atom, a bromine atom, an iodine atom or a hydrogen atom.
The A monomer is 3, 6-diamino-2, 5-benzenediol, 4, 6-diamino-1, 3-benzenediol, 1, 2-diamino-3, 6-benzenediol, 3, 5-diamino-2, 6-pyridinediol, 1, 5-diamino-4, 8-naphthalenediol, 3-dihydroxy-4, 4-biphenyldiamine or 1, 2-diamino-3, 8-naphthalenediol and hydrochloride thereof, and the structural formulas are as follows:
the monomer B is 2, 5-dihydroxybenzoquinone, 2, 5-dihydroxyl-6-chloranil, 2, 5-dihydroxyl-3, 6-chloranil, 2, 5-dihydroxyl-6-bromobenzoquinone, 2, 5-dihydroxyl-3, 6-dibromobenzoquinone, 2, 5-dihydroxyl-6-iodobenzoquinone or 2, 5-dihydroxyl-3, 6-diiodobenzoquinone, and the structural formulas are as follows:
the preparation method of the benzoxazinyl conjugated trapezoid polymer comprises the following specific steps:
the mole ratio of the monomer A to the monomer B is 1:1-1:1.2, adding an anhydrous high boiling point solvent into a polymerization reaction kettle, uniformly stirring, introducing argon, heating for reaction, and then cooling to room temperature. And then carrying out first post-treatment to obtain polymer precursor powder. And drying, taking polymer precursor powder, putting the polymer precursor powder into a vacuum atmosphere furnace for heating treatment, and then cooling the polymer precursor powder to room temperature. Finally, carrying out secondary post-treatment to obtain benzoxazine conjugated trapezoid polymer powder.
Wherein the anhydrous high boiling point solvent is anhydrous N, N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), hexamethylphosphoramide (HMPA), 1, 4-Dioxane (DO), diglyme (DGDE) or N, N-Dimethylformamide (DMF), etc.;
the reaction temperature is 100-160 ℃, the reaction time is 24-120h, and the argon flow rate is 30-100ml/min;
the first and second post treatments are pouring into centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 ℃ for 48 hours;
heating the polymer precursor powder in a vacuum atmosphere furnace at 280-350 deg.c for 2-5 hr at 5 deg.c/min and cooling to 30min at 5-10 deg.c.
The invention also provides application of the benzoxazinyl conjugated trapezoid polymer in preparing a benzoxazinyl conjugated trapezoid polymer gas sensing device for hydrogen sulfide detection.
The method comprises the following steps:
stirring benzoxazine-based conjugated trapezoid polymer powder in a low-boiling point solvent, uniformly dispersing the powder by ultrasonic, uniformly coating the powder on the surface of a substrate by using a microsyringe, and processing the powder in a constant temperature and humidity box to obtain a benzoxazine-based conjugated trapezoid polymer gas sensor;
the hydrogen sulfide response value of the assembled gas sensor device was tested by placing the device in an atmosphere of hydrogen sulfide gas.
Wherein the dosage of the benzoxazinyl conjugated trapezoid polymer powder is 10-100mg, preferably the low-boiling point solvent is dichloromethane, chloroform, ethyl acetate, methanol, ethanol, n-hexane or tetrahydrofuran, and the like, preferably the substrate is glass, ceramic, polyimide (PI), polyethylene terephthalate (PET) or an interdigital electrode, preferably the thickness of the organic semiconductor gas sensor is 50-500 micrometers, preferably the processing temperature of a constant temperature and humidity box is 40 ℃, the humidity is 15%, the time is 5h, and the concentration of hydrogen sulfide gas is 0-100ppm.
The invention has the advantages and beneficial effects that:
compared with the preparation method in the reference (2), the preparation method of the trapezoidal conductive polymer constructed based on the A monomer and the B monomer is simple and has lower cost. The prepared conjugated polymer has good conductivity and thermal stability. The method shows high specificity, high sensitivity, high recovery response, good thermal stability and good chemical stability of hydrogen sulfide detection. The benzoxazine-based conjugated trapezoid polymer has remarkable semiconductor characteristics, can work at room temperature, has low power consumption requirements, is possibly suitable for a wearable sensor or on-site rapid detection of acute toxicity and corrosive hydrogen sulfide gas, such as pipeline and sewage treatment, and can be used as a core material of a portable hydrogen sulfide tester, thereby having wide application prospects in the field of hydrogen sulfide detection.
Drawings
FIG. 1 shows the chemical reaction of monomers A and B to form benzoxazinyl-conjugated ladder polymers.
FIG. 2 shows the molecular chemical structural formula of the A monomer diaminobenzenediol.
FIG. 3 shows the chemical structural formula of B monomer benzoquinone compounds.
Fig. 4 is an infrared spectrum of a benzoxazinyl-conjugated ladder polymer.
Fig. 5 is a graph of response values of a benzoxazine-based conjugated trapezoidal polymer gas sensor device in different organic vapor atmospheres.
FIG. 6 is a graph of response versus recovery curves for a benzoxazine-based conjugated trapezoidal polymer gas sensor device at different hydrogen sulfide concentrations.
FIG. 7 is a graph showing the response of a benzoxazinyl-conjugated ladder polymer gas sensor device at 0-100ppm.
Detailed Description
Example 1:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
21.3 g of DAR (213.06) monomer and 24.9 g of chloranil acid (208.98) monomer B are added into a polymerization reaction kettle, 500ml of anhydrous NMP is added, the temperature is programmed to 140 ℃ after the mixture is vacuumized and ventilated for multiple times, the mixture is stirred uniformly, and argon gas (with the flow rate of 70 ml/min) is introduced. The reaction was carried out for 120h. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 10 g of the polymer powder was taken and placed in a vacuum atmosphere furnace, and the temperature was raised to 300℃for 2 hours. The procedure was then cooled to room temperature (30 min 10 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.c for 48 hr to obtain benzoxazine conjugated trapezoidal polymer powder. The polymer powder was tested by using a VECTORN22 type Fourier transform infrared spectrometer from Bruker company and plotted to obtain FIG. 4.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
and (3) stirring 10mg of polymer powder in a dichloromethane solvent, uniformly dispersing by ultrasonic, uniformly coating on the surface of an interdigital electrode substrate by using a microsyringe, and placing in a constant temperature (40 ℃) constant humidity (15%) box for 5 hours to obtain the organic semiconductor gas sensor device, wherein the thickness of the device is 50 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1) drawing a curve to obtain a response-recovery curve value of the common organic vapor selectivity in the hydrogen sulfide atmosphere of the graph 5 and 0-100ppm, and drawing a curve to obtain the graph 6.
Example 2:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
21.3 g of DAR (213.06) monomer and 20.8 g of chloranil acid (208.98) monomer are added into a polymerization reaction kettle, 450ml of anhydrous DMF is added, the temperature is programmed to be 100 ℃ after multiple times of ventilation, the mixture is stirred uniformly, and argon (flow rate of 30 ml/min) is introduced. The reaction was carried out for 24 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. The procedure was then cooled to room temperature (30 min5 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
100mg of polymer powder is taken, stirred in dichloromethane solvent and dispersed evenly by ultrasonic, and is evenly coated on the surface of an interdigital electrode substrate by a microsyringe, and the organic semiconductor gas sensor is obtained after 5 hours in a constant temperature (40 ℃) constant humidity (15%) box, and the thickness of the device is 500 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Example 3:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
14 g of 4, 6-diaminoresorcinol (140.138) monomer and 15.4 g of 2, 5-dihydroxybenzoquinone (140.09) monomer (B) are added into a polymerization reaction kettle, 480ml of anhydrous NMP is added, the temperature is programmed to 160 ℃ after multiple ventilation by vacuum pumping, stirring is uniform, and argon gas (flow rate 100 ml/min) is introduced. The reaction was carried out for 48 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 5 g of polymer powder is taken and placed in a vacuum atmosphere furnace, and the temperature is raised to 350 ℃ for 3 hours. The procedure was then cooled to room temperature (30 min5 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
50mg of polymer powder was stirred in a dichloromethane solvent and dispersed uniformly by ultrasoundAnd uniformly coating the organic semiconductor gas sensor on the surface of a glass substrate by using a microsyringe, and placing the organic semiconductor gas sensor in a constant temperature (40 ℃) constant humidity (15%) box for 5 hours, wherein the thickness of the organic semiconductor gas sensor is 200 micrometers. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Example 4:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
14 g of 4, 6-diaminoresorcinol (140.138) monomer and 14 g of 2, 5-dihydroxybenzoquinone (140.09) monomer (B) are added into a polymerization reaction kettle, 450ml of anhydrous NMP is added, the temperature is programmed to 160 ℃ after multiple ventilation by vacuum pumping, stirring is uniform, and argon gas (flow rate is 80 ml/min) is introduced. The reaction was carried out for 48 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 5 g of polymer powder is taken and placed in a vacuum atmosphere furnace, and the temperature is raised to 350 ℃ for 3 hours. The procedure was then cooled to room temperature (30 min5 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
and (3) stirring 50mg of polymer powder in an ethanol solvent, uniformly dispersing by ultrasonic, uniformly coating on the surface of a glass substrate by using a microsyringe, and placing in a constant temperature (40 ℃) constant humidity (15%) box for 5 hours to obtain the organic semiconductor gas sensor device, wherein the thickness of the device is 400 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Example 5:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
14 g of monomer A3, 6-diamino-2, 5-benzenediol (140.138) and 18.4 g of monomer B2, 5-dihydroxyl 6-chloranil (175.53) are added into a polymerization reaction kettle, 500ml of anhydrous DMAC is added, the temperature is programmed to 120 ℃ after the mixture is vacuumized and ventilated for many times, the mixture is stirred uniformly, and argon gas (the flow rate is 50 ml/min) is introduced. The reaction was carried out for 64h. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 6 g of polymer powder is taken and placed in a vacuum atmosphere furnace, and the temperature is raised to 320 ℃ for 4 hours. The procedure was then cooled to room temperature (30 min6 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
and (3) taking 100mg of polymer powder, stirring in an ethanol solvent, uniformly dispersing by ultrasonic, uniformly coating on the surface of a glass substrate by using a microsyringe, and placing in a constant temperature (40 ℃) constant humidity (15%) box for 5 hours to obtain the organic semiconductor gas sensor device, wherein the thickness of the device is 100 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Example 6:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
14 g of monomer A3, 6-diamino-2, 5-dihydroxybenzene (140.138) and 15.1 g of monomer B2, 5-dihydroxybenzoquinone (140.09) are added into a polymerization reaction kettle, 500ml of anhydrous DMAC is added, the temperature is programmed to 140 ℃ after the mixture is vacuumized and ventilated for many times, the mixture is stirred uniformly, and argon gas (the flow rate is 50 ml/min) is introduced. The reaction was carried out for 64h. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 6 g of polymer powder is taken and placed in a vacuum atmosphere furnace, and the temperature is raised to 320 ℃ for 4 hours. The procedure was then cooled to room temperature (30 min8 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
and stirring 80mg of polymer powder in an ethanol solvent, uniformly dispersing by ultrasonic, uniformly coating the polymer powder on the surface of a PI substrate by using a microsyringe, and placing the mixture in a constant temperature (40 ℃) constant humidity (15%) box for 5 hours to obtain the organic semiconductor gas sensor device, wherein the thickness of the device is 180 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Example 7:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
14 g of monomer A3, 6-diamino-2, 5-benzenediol (140.138) and 20.8 g of monomer B2, 5-dihydroxy-3, 6-dichlorobenzquinone (208.98) are added into a polymerization reaction kettle, 480ml of anhydrous NMP is added, the mixture is vacuumized and ventilated for multiple times, the temperature is programmed to 140 ℃, the mixture is stirred uniformly, and argon gas (the flow rate is 50 ml/min) is introduced. The reaction was carried out for 64h. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 6 g of polymer powder is taken and placed in a vacuum atmosphere furnace, and the temperature is raised to 320 ℃ for 4 hours. The procedure was then cooled to room temperature (30 min8 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
and stirring 80mg of polymer powder in an ethyl acetate solvent, uniformly dispersing by ultrasonic, uniformly coating the polymer powder on the surface of a PI substrate by using a microsyringe, and placing the mixture in a constant temperature (40 ℃) constant humidity (15%) box for 5 hours to obtain the organic semiconductor gas sensor device, wherein the thickness of the device is 150 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Example 8:
(1) A preparation method of a benzoxazinyl conjugated trapezoid polymer comprises the following steps:
14 g of 1, 2-diamino-3, 6-benzenediol (140.138) serving as a monomer A and 24.9 g of 2, 5-dihydroxy-3, 6-dichlorobenzquinone (208.98) serving as a monomer B are added into a polymerization reaction kettle, 450ml of anhydrous DMF is added, the mixture is vacuumized and ventilated for multiple times, the temperature is programmed to be 100 ℃, the mixture is stirred uniformly, and argon (the flow rate is 50 ml/min) is introduced. The reaction was carried out for 120h. After the reaction is finished, the reaction kettle is cooled to room temperature, poured into a centrifuge tube, added with ultrapure water for centrifugation, washed for 6 times, and washed with absolute ethyl alcohol for 3 times. Vacuum drying at 60℃for 48h. 10 g of the polymer powder was taken and placed in a vacuum atmosphere furnace, and the temperature was raised to 300℃for 4 hours. The procedure was then cooled to room temperature (30 min8 ℃). Pouring into a centrifuge tube, adding ultrapure water, centrifuging, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60℃for 48h. The benzoxazinyl conjugated trapezoid polymer powder can be obtained.
(2) The application of the benzoxazinyl conjugated trapezoid polymer in preparing the benzoxazinyl conjugated trapezoid polymer gas sensor for hydrogen sulfide detection comprises the following steps:
60mg of polymer powder is taken, stirred in ethyl acetate solvent and dispersed uniformly by ultrasonic, and uniformly coated on the surface of a PET substrate by a microsyringe, and the organic semiconductor gas sensor is obtained after 5 hours in a constant temperature (40 ℃) constant humidity (15%) box, and the thickness of the device is 80 microns. The hydrogen sulfide response value (R) of the assembled gas sensor device was measured by placing it in an atmosphere of hydrogen sulfide gas (0-100 ppm) air /R response -1)。
Claims (4)
1. The application of the benzoxazine-based conjugated trapezoid polymer in preparing a benzoxazine-based conjugated trapezoid polymer gas sensor for hydrogen sulfide detection is characterized in that the method comprises the following steps:
stirring benzoxazine-based conjugated trapezoid polymer powder in a low-boiling point solvent, uniformly dispersing the powder by ultrasonic, uniformly coating the powder on the surface of a substrate by using a microsyringe, and processing the powder in a constant temperature and humidity box to obtain a benzoxazine-based conjugated trapezoid polymer gas sensor;
placing the assembled gas sensor device in the atmosphere of hydrogen sulfide gas, and testing the hydrogen sulfide response value;
the preparation method of the benzoxazinyl conjugated trapezoid polymer comprises the steps of taking diaminobenzenediol molecules as A monomers, taking benzoquinone compounds as B monomers, carrying out polymerization reaction in a polymerization reaction kettle, then carrying out vacuum drying, and finally carrying out heat treatment in a vacuum atmosphere furnace to form a ring, thereby obtaining the benzoxazinyl conjugated trapezoid polymer, wherein the structural formula of the polymer is shown as follows
Wherein the R group is a chlorine atom, a bromine atom, an iodine atom or a hydrogen atom;
the preparation method comprises the following specific steps:
the molar ratio was set to 1:1-1:1.2, adding the monomer A and the monomer B into a polymerization reaction kettle, adding an anhydrous high-boiling point solvent, uniformly stirring, introducing argon, reacting for 24-120 hours at a reaction temperature of 100-160 ℃, cooling to room temperature, performing first post-treatment to obtain polymer precursor powder, drying, placing the polymer precursor powder into a vacuum atmosphere furnace at 280-350 ℃ for 2-5 hours, heating at a speed of 5 ℃/min, cooling to room temperature, and performing second post-treatment to obtain benzoxazine-conjugated trapezoid polymer powder;
wherein the structural formula of the A monomer 3, 6-diamino-2, 5-benzenediol is as follows:
wherein the B monomer comprises 2, 5-dihydroxybenzoquinone, 2, 5-dihydroxyl-6-chloranil, 2, 5-dihydroxyl-3, 6-chloranil, 2, 5-dihydroxyl-6-bromobenzoquinone, 2, 5-dihydroxyl-3, 6-dibromobenzoquinone, 2, 5-dihydroxyl-6-iodobenzoquinone or 2, 5-dihydroxyl-3, 6-diiodobenzoquinone, and the structural formulas are as follows:
2. the use according to claim 1, wherein,
the anhydrous high boiling point solvent is anhydrous N, N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), hexamethylphosphoramide (HMPA), 1, 4-Dioxane (DO), diglyme (DGDE) or N, N-Dimethylformamide (DMF);
argon flow rate is 30-100ml/min, and the procedure is cooled to room temperature for 30min and 5-10 ℃;
the first and second post treatments are pouring into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, washing for 3 times with absolute ethyl alcohol, and vacuum drying at 60 ℃ for 48 hours.
3. The use according to claim 1, wherein the benzoxazine-based conjugated trapezoidal polymer powder is used in an amount of 10-100mg;
the substrate is glass, ceramic, polyimide (PI), polyethylene terephthalate (PET) or an interdigital electrode;
the thickness of the benzoxazine-based conjugated trapezoid polymer gas sensor is 50-500 micrometers;
the temperature in the constant temperature and humidity box is 40 ℃, the humidity is 15%, and the time is 5 hours;
the concentration of the hydrogen sulfide gas is 0-100ppm.
4. Use according to claim 1, wherein the low boiling solvent is dichloromethane, chloroform, ethyl acetate, methanol, ethanol, n-hexane or tetrahydrofuran.
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