CN114672020A - Preparation method of benzoxazine-based conjugated trapezoidal polymer and application of benzoxazine-based conjugated trapezoidal polymer in hydrogen sulfide detection - Google Patents
Preparation method of benzoxazine-based conjugated trapezoidal polymer and application of benzoxazine-based conjugated trapezoidal polymer in hydrogen sulfide detection Download PDFInfo
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Abstract
A preparation method of a benzoxazine-based conjugated ladder-shaped polymer and application thereof in hydrogen sulfide detection. The benzoxazinyl conjugated trapezoidal polymer takes diaminobenzenediphenol molecules as an A monomer and a benzoquinone compound as a B monomer, and is prepared into a polybenzoxazine trapezoidal conductive polymer through a polymerization reaction kettle and a vacuum atmosphere furnace, and then a gas sensor is prepared for detecting acid gases such as hydrogen sulfide. The invention has the advantages of simple preparation of the polymer, lower cost, high specificity and high sensitivity of hydrogen sulfide detection. The benzoxazine-based conjugated trapezoidal polymer has remarkable semiconductor characteristics, can work at room temperature, has low power consumption requirement, is possibly suitable for wearable sensors or field rapid detection of acute toxic and corrosive hydrogen sulfide gas, such as pipeline and sewage treatment, and also can be used as a core material of a portable hydrogen sulfide tester, thereby having wide application prospect 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-based conjugated trapezoidal polymer and application of the benzoxazine-based conjugated trapezoidal polymer in hydrogen sulfide detection.
Background
Hydrogen sulfide is a highly corrosive contaminant gas that is prevalent in natural gas streams and can also be produced by anaerobic bacterial decomposition of organic matter. According to the regulations of the national institute for occupational safety and health, hydrogen sulfide allows human body contact in a limited amount of about 20ppm, over 100ppm being directly dangerous to life, and has acute toxicity, which has prompted the development of low-cost and portable sensing technology that can rapidly identify trace concentrations of hydrogen sulfide in environments such as mines, natural gas pipelines, and sewage treatment plants. Therefore, the detection of exogenous hydrogen sulfide has attracted considerable research interest, and the research on hydrogen sulfide sensors is also rapidly developing. Reference is made to the literature: (1) m < t > e J.Bezdek, Luo S X L, Ku K H, et al.A chemistive methane sensor [ J ] Proceedings of the National Academy of Sciences,2021,118(2) e 2022515118. The on-site hydrogen sulfide detection method mainly comprises two methods: firstly, the hydrogen sulfide concentration can be obtained by directly sampling and sending the sample into a laboratory and performing energy spectrum analysis by using a gas chromatograph, the method has high accuracy, but the method belongs to single-point test, has large sampling and sample measuring workload, long period and relatively high cost, and is difficult to reflect the instantaneous change rule of the hydrogen sulfide in time; and secondly, hydrogen sulfide on-line detection equipment is installed to detect the dynamic change of the concentration of hydrogen sulfide in real time, and the method is high in accuracy, expensive and suitable for a sulfur-containing gas field with concentrated hydrogen sulfide gas well distribution and relatively high hydrogen sulfide concentration. At present, aiming at the detection of low-concentration hydrogen sulfide, a portable hydrogen sulfide tester is adopted to carry out open-air real-time multipoint detection at a wellhead or a gas gathering station, and the method has the advantages of convenient operation and lower cost. Most of the core materials of the existing portable hydrogen sulfide tester 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 low requirements on manufacturing equipment and low cost, so that research on the hydrogen sulfide response high polymer of the core material of the portable hydrogen sulfide tester is carried out at the same time.
According to the research literature, a trapezoidal polybenzoxazine polymer is synthesized through 1, 4-p-phenylenediamine and chloranil at Gong Chung (the university of southeast of the year 2016), but the performance of the polybenzoxazine polymer serving as a supercapacitor material is mainly researched, the hydrogen sulfide detection performance is not mentioned, and the preparation method in the patent is different from the Gong Chung preparation method and is different from the application. Reference is made to the literature: (2) gong X, Zhang Y, Wen H, et al, Phenoxazine-Based Conjugated Materials for Supercapacitors [ J ]. Chem Electrochem,2016,3(11):1837-1846.(3) Gong-Chunghui-triphenyldioxazine photoelectric material design, synthesis and performance study [ D ]. southeast university, 2016.
Disclosure of Invention
The invention aims to provide a preparation method of a benzoxazine-based conjugated trapezoidal polymer and application thereof in hydrogen sulfide detection aiming at the technical analysis and problems.
The technical scheme of the invention is as follows:
a preparation method of a benzoxazine-based conjugated ladder-shaped polymer comprises the steps of carrying out polymerization reaction on the benzoxazine-based conjugated ladder-shaped polymer by taking a diamino-benzenediol molecule as an A monomer and a benzoquinone compound as a B monomer, and carrying out heat treatment in a vacuum drying vacuum atmosphere furnace to form a ring, so as to generate the benzoxazine-based conjugated ladder-shaped 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 monomer A 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 respectively as follows:
the monomer B is 2, 5-dihydroxy-benzoquinone, 2, 5-dihydroxy-6-chloranil, 2, 5-dihydroxy-3, 6-dichlorobenzoquinone, 2, 5-dihydroxy-6-bromobenzoquinone, 2, 5-dihydroxy-3, 6-dibromobenzoquinone, 2, 5-dihydroxy-6-iodobenzoquinone or 2, 5-dihydroxy-3, 6-diiodobenzoquinone, and the structural formulas of the monomers are respectively as follows:
the preparation method of the benzoxazine-based conjugated trapezoidal polymer comprises the following specific steps:
mixing the monomer A and the monomer B according to a molar ratio of 1: 1-1: 1.2, adding the mixture into a polymerization reaction kettle, adding an anhydrous high-boiling-point solvent, uniformly stirring, introducing argon, heating for reaction, and then cooling to room temperature. Then carrying out first post-treatment to obtain polymer precursor powder. And after drying, putting the polymer precursor powder into a vacuum atmosphere furnace for heating treatment, and then, cooling the procedure to room temperature. And finally, carrying out secondary post-treatment to obtain the benzoxazine-based conjugated trapezoidal 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), N-Dimethylformamide (DMF), etc.;
the reaction temperature is 100-160 ℃, the time is 24-120h, and the flow rate of argon is 30-100 ml/min;
the first and second post-treatments are poured into a centrifuge tube, ultrapure water is added for centrifugation, and the centrifuge tube is washed for 6 times, and is washed for 3 times by absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h;
the heating temperature of the polymer precursor powder in a vacuum atmosphere furnace is 280-350 ℃, the maintaining time is 2-5h, the heating rate is 5 ℃/min, and the temperature is reduced to 30min and 5-10 ℃ in a program.
The invention also provides application of the benzoxazine-based conjugated trapezoidal polymer in preparation of a benzoxazine-based conjugated trapezoidal polymer gas sensing device for detecting hydrogen sulfide.
The method comprises the following steps:
stirring benzoxazine-based conjugated trapezoidal polymer powder in a low-boiling-point solvent, uniformly dispersing the benzoxazine-based conjugated trapezoidal polymer powder by ultrasonic, uniformly coating the benzoxazine-based conjugated trapezoidal polymer powder on the surface of a substrate by using a microsyringe, and treating the benzoxazine-based conjugated trapezoidal polymer powder in a constant temperature and humidity chamber to obtain a benzoxazine-based conjugated trapezoidal polymer gas sensing device;
and placing the assembled gas sensing device in an atmosphere of hydrogen sulfide gas, and testing the hydrogen sulfide response value of the gas sensing device.
The benzoxazine-based conjugated trapezoidal polymer powder is 10-100mg, preferably, a low-boiling-point solvent is dichloromethane, chloroform, ethyl acetate, methanol, ethanol, n-hexane or tetrahydrofuran, and the like, preferably, a substrate is glass, ceramic, Polyimide (PI), polyethylene terephthalate (PET) or an interdigital electrode, preferably, the thickness of an organic semiconductor gas sensing device is 50-500 micrometers, preferably, the processing temperature of a constant temperature and humidity chamber is 40 ℃, the humidity is 15%, the time is 5 hours, and preferably, the concentration of hydrogen sulfide gas is 0-100 ppm.
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 monomer A and the monomer B is simple and low in cost. The prepared conjugated polymer has good conductivity and thermal stability. It exhibits high specificity, high sensitivity, high recovery responsiveness, good thermal stability and good chemical stability for hydrogen sulfide detection. The benzoxazine-based conjugated trapezoidal polymer has remarkable semiconductor characteristics, can work at room temperature, has low power consumption requirement, is possibly suitable for wearable sensors or field rapid detection of acute toxic and corrosive hydrogen sulfide gas, such as pipeline and sewage treatment, and also can be used as a core material of a portable hydrogen sulfide tester, so that the benzoxazine-based conjugated trapezoidal polymer has wide application prospect in the field of hydrogen sulfide detection.
Drawings
FIG. 1 shows the chemical reaction formula of monomer A and monomer B to generate a benzoxazine-based conjugated ladder polymer.
FIG. 2 shows the chemical structural formula of monomer A, diaminobenzenediol.
FIG. 3 is the chemical structure of monomer benzoquinone compound B.
FIG. 4 shows an IR spectrum of a benzoxazinyl-based conjugated ladder polymer.
Fig. 5 shows response values of the benzoxazinyl-based conjugated trapezoidal polymer gas sensing device in different organic vapor atmospheres.
FIG. 6 is a response-recovery curve of the benzoxazine-based conjugated trapezoidal polymer gas sensing device under different hydrogen sulfide concentrations.
FIG. 7 shows the response values of the benzoxazine-based conjugated trapezoidal polymer gas sensing device at 0-100 ppm.
Detailed Description
Example 1:
(1) a preparation method of a benzoxazine-based conjugated trapezoidal polymer comprises the following steps:
21.3 g of monomer A DAR (213.06) and 24.9 g of monomer B chloranilic acid (208.98) were added to a polymerization kettle, 500ml of anhydrous NMP was added, after evacuation and multiple purging, the temperature was programmed to 140 ℃, stirring was carried out, and argon gas was introduced (flow rate 70 ml/min). And reacting for 120 h. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 10 g of polymer powder was placed in a vacuum atmosphere furnace and the temperature was programmed to 300 ℃ for 2 h. Then the program was allowed to cool to room temperature (30min 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 for 48h at 60 ℃ to obtain benzoxazine-based conjugated trapezoidal polymer powder. The polymer powder was tested by means of a Fourier transform infrared spectrometer model VECTORN22 from Bruker and plotted to obtain FIG. 4.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
10mg of polymer powder is stirred in a dichloromethane solvent and uniformly dispersed by ultrasonic, a microsyringe is uniformly coated on the surface of the interdigital electrode substrate, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5h, wherein the thickness of the device is 50 micrometers. Placing the gas-sensing device in a hydrogen sulfide gasThe hydrogen sulfide response value (R) of the alloy is tested in an atmosphere (0-100ppm)air/Rresponse-1) and plotting a curve to obtain figure 7, a common organic vapor selectivity response value and plotting a curve to obtain figure 5, a response-recovery curve value under a hydrogen sulfide atmosphere of 0-100ppm and plotting a curve to obtain figure 6.
Example 2:
(1) a preparation method of a benzoxazine-based conjugated ladder-shaped polymer comprises the following steps:
21.3 g of monomer A DAR (213.06) and 20.8 g of monomer B chloranilic acid (208.98) are added into a polymerization kettle, 450ml of anhydrous DMF is added, after vacuumizing for a plurality of times and air exchange, the temperature is programmed to 100 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 30 ml/min). And reacting for 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle 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 h. The program was then allowed to cool to room temperature (30min5 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
100mg of polymer powder is stirred in a dichloromethane solvent and uniformly dispersed by ultrasonic, a microsyringe is uniformly coated on the surface of an interdigital electrode substrate, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5 hours, wherein the thickness of the device is 500 micrometers. The loaded gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm), and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Example 3:
(1) a preparation method of a benzoxazine-based conjugated trapezoidal polymer comprises the following steps:
14 g of A monomer 4, 6-diaminoresorcinol (140.138) and 15.4 g of B monomer 2, 5-dihydroxy benzoquinone (140.09) are added into a polymerization reaction kettle, 480ml of anhydrous NMP is added, after vacuumizing and air exchange are carried out for many times, the temperature is programmed to 160 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 100 ml/min). And reacting for 48 hours. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 5 g of polymer powder is put into a vacuum atmosphere furnace and the temperature is programmed to 350 ℃ for 3 h. The program was then allowed to cool to room temperature (30min5 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
50mg of polymer powder is stirred in a dichloromethane solvent and uniformly dispersed by ultrasonic, a microsyringe is uniformly coated on the surface of a glass substrate, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5 hours, wherein the thickness of the device is 200 microns. The loaded gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm), and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Example 4:
(1) a preparation method of a benzoxazine-based conjugated trapezoidal polymer comprises the following steps:
14 g of A monomer 4, 6-diaminoresorcinol (140.138) and 14 g of B monomer 2, 5-dihydroxy benzoquinone (140.09) are added into a polymerization reaction kettle, 450ml of anhydrous NMP is added, after vacuumizing for a plurality of times and air exchange, the temperature is programmed to 160 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 80 ml/min). And reacting for 48 hours. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 5 g of polymer powder is put into a vacuum atmosphere furnace and the temperature is programmed to 350 ℃ for 3 h. The program was then allowed to cool to room temperature (30min5 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
50mg of polymer powder is stirred in an ethanol solvent and uniformly dispersed by ultrasonic, a microsyringe is uniformly coated on the surface of a glass substrate, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5 hours, wherein the thickness of the device is 400 microns. The loaded gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm), and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Example 5:
(1) a preparation method of a benzoxazine-based conjugated trapezoidal polymer comprises the following steps:
14 g of monomer A, 3, 6-diamino-2, 5-benzenediol (140.138) and 18.4 g of monomer B, 2, 5-dihydroxy 6-chloranil (175.53) are added into a polymerization reaction kettle, 500ml of anhydrous DMAC is added, after vacuumizing and air exchange for many times, the temperature is programmed to 120 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 50 ml/min). The reaction was carried out for 64 h. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 6 g of polymer powder are taken and put into a vacuum atmosphere furnace, and the temperature is programmed to 320 ℃ for 4 h. The program was then allowed to cool to room temperature (30min6 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated trapezoidal polymer in preparing a benzoxazine-based conjugated trapezoidal polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
100mg of polymer powder is taken to be stirred in an ethanol solvent and dispersed uniformly by ultrasonic, a microsyringe is used for coating the surface of a glass substrate uniformly, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5 hours, wherein the thickness of the device is 100 micrometers. The loaded gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm), and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Example 6:
(1) a preparation method of a benzoxazine-based conjugated trapezoidal polymer comprises the following steps:
14 g of monomer A, 3, 6-diamino-2, 5-benzenediol (140.138) and 15.1 g of monomer B, 2, 5-dihydroxy benzoquinone (140.09) are added into a polymerization reaction kettle, 500ml of anhydrous DMAC is added, after vacuumizing and air exchange for many times, the temperature is programmed to 140 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 50 ml/min). The reaction was carried out for 64 h. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 6 g of polymer powder are taken and put into a vacuum atmosphere furnace, and the temperature is programmed to 320 ℃ for 4 h. The program was then allowed to cool to room temperature (30min8 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
80mg of polymer powder is taken to be stirred in an ethanol solvent and uniformly dispersed by ultrasonic, a micro-sampler is uniformly coated on the surface of a PI substrate, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5h, wherein the thickness of the device is 180 micrometers. The loaded gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm), and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Example 7:
(1) a preparation method of a benzoxazine-based conjugated trapezoidal polymer comprises the following steps:
14 g of monomer A, 3, 6-diamino-2, 5-benzenediol (140.138) and 20.8 g of monomer B, 2, 5-dihydroxy-3, 6-dichlorobenzoquinone (208.98) are added into a polymerization reaction kettle, 480ml of anhydrous NMP is added, after vacuumizing for many times and air exchange, the temperature is programmed to 140 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 50 ml/min). The reaction was carried out for 64 h. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 6 g of polymer powder are taken and put into a vacuum atmosphere furnace, and the temperature is programmed to 320 ℃ for 4 h. The program was then allowed to cool to room temperature (30min8 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
80mg of polymer powder is taken to be stirred in ethyl acetate solvent and uniformly dispersed by ultrasonic, a micro-sampler is uniformly coated on the surface of a PI substrate, and the organic semiconductor gas sensing device is obtained in a constant temperature (40 ℃) and constant humidity (15%) box for 5h, wherein the thickness of the device is 150 micrometers. The gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm) and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Example 8:
(1) a preparation method of a benzoxazine-based conjugated ladder-shaped polymer comprises the following steps:
14 g of monomer A, 1, 2-diamino-3, 6-benzenediol (140.138) and 24.9 g of monomer B, 2, 5-dihydroxy-3, 6-dichlorobenzoquinone (208.98) are added into a polymerization reaction kettle, 450ml of anhydrous DMF is added, after vacuumizing for many times and air exchange, the temperature is programmed to 100 ℃, the mixture is stirred uniformly, and argon is introduced (the flow rate is 50 ml/min). And reacting for 120 h. After the reaction is finished, cooling the reaction kettle to room temperature, pouring the reaction kettle into a centrifuge tube, adding ultrapure water for centrifugation, washing for 6 times, and washing for 3 times with absolute ethyl alcohol. Vacuum drying at 60 deg.C for 48 h. 10 g of polymer powder was placed in a vacuum atmosphere furnace and the temperature was programmed to 300 ℃ for 4 h. The program was then allowed to cool to room temperature (30min8 ℃). 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 h. So as to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
(2) The application of the benzoxazine-based conjugated ladder-shaped polymer in preparing a benzoxazine-based conjugated ladder-shaped polymer gas sensing device for detecting hydrogen sulfide comprises the following steps:
60mg of polymer powder is taken and stirred in ethyl acetate solvent and evenly dispersed by ultrasonic, a microsyringe is evenly coated on the surface of a PET substrate, and the temperature is constant (40 ℃) and constantAnd 5h in a wet (15%) box is the organic semiconductor gas sensing device, and the thickness of the device is 80 micrometers. The gas sensor device was placed in an atmosphere of hydrogen sulfide gas (0-100ppm) and the hydrogen sulfide response value (R) was measuredair/Rresponse-1)。
Claims (8)
1. A preparation method of a benzoxazine-based conjugated ladder-shaped polymer is characterized by comprising the following steps: the benzoxazinyl conjugated trapezoidal polymer takes diamino benzenediol molecules as A monomers and benzoquinone compounds as B monomers, is subjected to polymerization reaction in a polymerization reaction kettle, then is subjected to vacuum drying, and finally is subjected to heat treatment in a vacuum atmosphere furnace to form a ring, so that the benzoxazinyl conjugated trapezoidal polymer is generated, wherein the structural formula of the polymer is shown as the following
Wherein the R group is a chlorine atom, a bromine atom, an iodine atom or a hydrogen atom.
2. The method of claim 1, wherein the a monomer comprises 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 salts thereof, wherein the structural formulas of the a monomer are as follows:
3. The method for preparing a benzoxazine-based conjugated ladder polymer according to claim 1, wherein the B monomer comprises 2, 5-dihydroxybenzoquinone, 2, 5-dihydroxy-6-chlorobenzoquinone, 2, 5-dihydroxy-3, 6-dichlorobenzoquinone, 2, 5-dihydroxy-6-bromobenzoquinone, 2, 5-dihydroxy-3, 6-dibromobenzoquinone, 2, 5-dihydroxy-6-iodobenzoquinone or 2, 5-dihydroxy-3, 6-diiodobenzoquinone, which have the following structural formulas:
4. the method for preparing the benzoxazine-based conjugated ladder-shaped polymer according to claim 1, comprising the following specific steps:
mixing the components in a molar ratio of 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 at the reaction temperature of 100-160 ℃ for 24-120h, 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 the temperature of 280-350 ℃ for 2-5h, wherein the heating rate is 5 ℃/min, performing post-program cooling to room temperature, and finally performing second post-treatment to obtain the benzoxazine-based conjugated trapezoidal polymer powder.
5. The production method according to claim 4,
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);
The flow rate of argon gas is 30-100ml/min, and the temperature is reduced to room temperature for 30min5-10 ℃;
the first and second post-treatments are poured into a centrifuge tube, ultrapure water is added for centrifugation, the centrifuge tube is washed for 6 times, absolute ethyl alcohol is used for washing for 3 times, and vacuum drying is carried out for 48 hours at 60 ℃.
6. Use of a benzoxazine-based conjugated ladder polymer prepared by the method of claim 1 in the preparation of a benzoxazine-based conjugated ladder polymer gas sensing device for hydrogen sulfide detection.
7. The use according to claim 6, characterized in that the method is:
stirring benzoxazine-based conjugated trapezoidal polymer powder in a low-boiling-point solvent, uniformly dispersing the benzoxazine-based conjugated trapezoidal polymer powder by ultrasonic, uniformly coating the benzoxazine-based conjugated trapezoidal polymer powder on the surface of a substrate by using a microsyringe, and treating the benzoxazine-based conjugated trapezoidal polymer powder in a constant temperature and humidity chamber to obtain a benzoxazine-based conjugated trapezoidal polymer gas sensing device;
and placing the assembled gas sensing device in an atmosphere of hydrogen sulfide gas, and testing the hydrogen sulfide response value of the gas sensing device.
8. The use according to claim 7, wherein the benzoxazine-based conjugated ladder polymer powder is used in an amount of 10-100mg, and the preferred low boiling solvent is dichloromethane, chloroform, ethyl acetate, methanol, ethanol, n-hexane or tetrahydrofuran;
The substrate is glass, ceramic, Polyimide (PI), polyethylene terephthalate (PET) or interdigital electrodes;
the thickness of the benzoxazine conjugated trapezoidal polymer gas sensing device is 50-500 micrometers;
the temperature and humidity in the constant temperature and humidity chamber are 40 deg.C and 15% for 5h
The concentration of hydrogen sulfide gas is 0-100 ppm.
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