Fluorine-containing polymer of specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer as well as preparation method and application of fluorine-containing polymer

Abstract

The invention relates to a fluorine-containing polymer of a specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer as well as a preparation method and application of the fluorine-containing polymer, and belongs to the technical field of fluorescent probes. The method specifically comprises the step of synthesizing a polymer with fluorine atoms as a solid fluorescence sensor probe. The probe realizes the detection of explosives through the interaction between fluorine atoms and nitryl and by doping CdSe / ZnS quantum dots. Based on the fluorine-containing polymer, aromatic alkyl hydrocarbon explosives (tracers) containing a single nitro group can be specifically recognized. Quantum dots are blended with the fluorine polymer, the quantum dots as a nano material are mixed and dispersed with the polymer to form a nanofiber membrane, and the fluorescence of the fluorine-containing quantum dot polymer is changed by further utilizing the interaction between fluorine and silicon atoms and nitro aromatic hydrocarbon, so that the fluorescence of the fluorine-containing quantum dot polymer is changed. Therefore, the specific detection-fluorescence rise of the mononitroalkane explosive is realized (fluorescence decline caused by interference such as light blocking is avoided).

Description

Technical Field

[0001] This application relates to the technical field of fluorescent probes, and in particular to a fluorine-containing polymer for a specific mono-nitroalkylbenzene aromatic hydrocarbon explosive tracer, and a preparation method and application thereof. Background Art

[0002] With the diversified development of high-energy density materials, nitroarenes with dual functions of explosives and markers are colorless and have low vapor pressure, etc., making them vulnerable to illegal use and difficult to identify. Specific recognition faces major challenges, and there is an urgent need to develop efficient and accurate detection technologies.

[0003] In a fluorescence detection system, the synergistic effect of conjugated polymers (CPs) and quantum dots can significantly improve the detection performance. Quantum dots, with their size-tunable luminescence characteristics, quantum yield of over 60%, and excellent photostability, combined with the molecular wire effect of CPs, make the sensitivity of the composite system comparable to that of police dogs, and it has the advantages of low cost and easy preparation. By surface functional modification of quantum dots, the electron transfer efficiency to nitro groups can be enhanced directionally, realizing the selective discrimination of nitrotoluene and nitroamine compounds.

[0004] Generally speaking, the electron-deficient characteristics of nitroarene explosives (such as TNT, DNT, etc.) enable specific recognition through dipole-dipole interactions. Typical military explosive mixtures have common characteristics: Composition C-2 / C-3 contains nitrotoluene (NT), while Amatol, Comp B, etc. are mainly composed of TNT / RDX. Since NT is widely used as an explosive label indicator (such as PETN-based systems like Detasheet), its detection has double verification value: it can not only trace the labeled explosives but also identify traditional energetic systems. This detection strategy based on structural commonalities has the dual advantages of reducing the false alarm rate and improving the detection accuracy.

[0005] Meanwhile, for the classification function of user requirements - explosives, materials capable of transferring the test of nitrobenzenes need to be developed. For example, Professor Callum J. McHug's ACS Appl. Mater. Interfaces, 2023, 15, 27915 - 27927 describes a small molecule fluorescent material whose fluorescence increases when detecting nitrotoluene and dinitrobenzene. Others such as J. Photochem. Photobiol. A: Chem., 2022, 428, 113865. Also, Subodh Kumar elaborates in Ratiometric fluorescence “Turn On” probe for fast and selective detection of TNT in solution, solid and vapour that the interaction between UREA - TP and TNT leads to fluorescence quenching in the molecular dissolved state, while fluorescence enhancement is exhibited in the aggregated state. Jung Su Park's J. Am. Chem. Soc. 2020, 142, 19579 - 19587 reports a series of dynamic fluorescence detection systems responsive to nitrogen - aromatic explosives (NACs), capable of achieving “turn - on” fluorescence sensing, showing higher sensitivity and selectivity. Compared with the fluorescence quenching principle, the enhancement method can exclude the fluorescence decline caused by photo - oxidation, light occlusion, and photo - aging, eliminate interference, prevent false alarms, and relatively has specificity, being able to classify a certain type of explosive singly.

[0006] In the field of quantum dots, as reported in Itamar Willner's Adv. Mater. 2012, 24, 6416 - 6421; Ivan P. Parkin's ACS Nano, 2016, 10, 1139 - 1146; Tian Cai Zhang's Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, 70, 2, 247 - 252; and Rafael Abargues' ACS Appl. Nano Mater. 2022, 5, 6717 - 6725. These researchers have carried out a series of studies on the application of quantum dots in explosive detection, providing new ideas. However, these findings still have problems such as irreversible signals, mismatch between the vapor diffusion rate and the adsorption energy barrier on the surface of quantum dots, and a sharp drop in the charge transfer efficiency at the polymer - quantum dot interface in the gaseous environment. Therefore, developing a universal probe based on the principle of fluorescence enhancement, with fast response, good recoverability, high sensitivity, wide detection range, and strong anti - interference ability, has important practical significance. If quantum dots can be combined with fluorescent polymers, it may provide an effective way for the detection of various nitro - containing explosives. Summary of the Invention

[0007] In view of this, the present application provides a fluorine - containing polymer for a specific mono - nitroalkylbenzene aromatic hydrocarbon explosive tracer, its preparation method and application. Based on this fluorine - containing polymer, it can specifically identify aromatic alkyl hydrocarbon explosives (tracers) containing a single nitro group, and can effectively overcome the defects existing in the above - mentioned prior art.

[0008] In the first aspect of the present application, a fluorine - containing polymer for a specific mono - nitroalkylbenzene aromatic hydrocarbon explosive tracer is provided. The structural formula of the fluorine - containing polymer is:

[0009]

[0010] Wherein, A is a third - type monomer or a fifth - type monomer, and both the third - type monomer and the fifth - type monomer are diyne monomers; B is a first - type monomer or a fourth - type monomer; C is a first - type monomer or a fourth - type monomer; E is a second - type monomer; F is a first - type monomer or a fourth - type monomer;

[0011] a, b, c, and d represent the number of different monomers linked in the reaction product.

[0012] Specifically, when selecting monomers, it is preferred that B and C are different monomers, and B and F are also different monomers.

[0013] Preferably, the structural formula of the first - type monomer is selected from one or more of the following:

[0014]

[0015] Among them, Y is Br or I. Among them, Y is Br or I. Specifically, the structural formulas all contain F at the ortho or meta position of the benzene ring Y, and it is possible that N is connected to an electron-withdrawing benzene ring (CF3 / NO2 / CN / F).

[0016] Preferably, the structural formula of the second type of monomer is selected from one or more of the following:

[0017]

[0018] Among them, X is C or Si; R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; Z is O, N, NH or S.

[0019] Specifically, when X is Si, the R linked to it can be H.

[0020] Preferably, the structural formula of the third type of monomer is selected from one or more of the following:

[0021]

[0022] Among them, X is C or Si; R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; Y is Br or I.

[0023] Preferably, the structural formula of the fourth type of monomer is selected from one or more of the following:

[0024]

[0025] Among them, Y is Br or I; R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; the PEG chain has a structure containing multiple -OCH2CH2- repeating units.

[0026] Preferably, the structural formula of the fifth type of monomer is selected from one or more of the following:

[0027]

[0028] Among them, R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; the PEG chain has a structure containing multiple -OCH2CH2- repeating units.

[0029] Preferably, the structural formula of the fluorine-containing polymer is:

[0030]

[0031] Wherein, X is C or Si; M is OR, NR2 or PEG, and the PEG chain has a structure containing multiple -OCH2CH2- repeating units; when it is a non-spiro fluorene structure, R is alkyl C n H 2n+1 , alkenyl, alkynyl, fluorenyl or fluorenyl with heteroatoms, where n is an integer within 1 - 25; when X is Si, the R linked thereto can be H, and the illustrated ring may or may not exist, and when it exists, it is fluorenyl.

[0032] It should be noted that: 1. The fluorine-containing first type of monomer is the core monomer; 2. a, b, c, d represent the numbers of different monomers linked by the reaction product; 3. X is C, Si, preferably Si, Z is O, N (depending on the valence bond, it can also be NH), S, preferably O, Y is Br, I, preferably I; 4. In particular, the PEG chain has a structure containing multiple -OCH2CH2- repeating units; 5. The above R is generally alkyl (C n H 2n+1 ), where n is an integer within 1 - 25, and in particular, when X is Si, the R linked thereto can be H; 6. The above fifth type of monomer is prepared from the fourth type of monomer.

[0033] The second aspect of the present application also provides a preparation method of a fluorine-containing polymer of the above-mentioned specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer, including the following synthetic route:

[0034]

[0035] The third aspect of the present application also provides an application of the fluorine-containing polymer of the above-mentioned specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer in the field of explosive detection.

[0036] Compared with the prior art, the present application has the following beneficial effects:

[0037] This application relates to the application of organic fluorescent polymers in the field of explosive detection, specifically including the synthesis of a polymer with fluorine atoms as a solid fluorescent sensor probe. This probe realizes the detection of explosives through the interaction between fluorine atoms and nitro groups and by doping CdSe / ZnS quantum dots. Based on such fluorine-containing polymers, aromatic alkyl hydrocarbon explosives (tracers) containing a single nitro group can be specifically recognized. By blending the quantum dots with this fluorine-containing polymer, the quantum dots are mixed and dispersed as nanomaterials with the polymer to form a nanofiber membrane. Further, by utilizing the interaction between fluorine and silicon atoms and nitroaromatic hydrocarbons, the fluorescence of the fluorine-containing quantum dot polymer changes, thereby realizing the specific detection of mononitroalkane explosives - fluorescence enhancement (avoiding fluorescence decline caused by interference such as light blocking). This method can also be combined with characteristics such as response time to identify explosives such as nitrotoluene, nitro-xylene, nitropolyxylene, and nitrobenzene. The construction of a sensor array helps to distinguish different types of nitro explosives. The detection sensitivity of this technology is extremely high, and the lowest detection limit can be as low as 1 ng (calculated based on nitrotoluene). In addition, since quantum dots are inorganic substances with high durability and act as anti-quenching agents to a certain extent, the polymer exhibits excellent resistance to photooxidative quenching (i.e., anti-photobleaching) in the test environment and has strong fluorescence self-healing with slow recovery. In continuous tests on pure explosives, this material maintains stability (it can be continuously tested more than 100 times), has a large number of recycling times and is not easily damaged, and is suitable for on-site alarms and vapor sensing in various harsh environments. The fluorescence response of the polymer is fluorescence enhancement type, which helps to effectively exclude interference from liquids such as water, toilet water, and hand cream. This method has many advantages such as specificity, fast response speed, good recoverability, high sensitivity, wide detection range, and strong anti-interference ability. Description of the Drawings

[0038] In order to more clearly illustrate the technical solutions in this application or the prior art, the following will briefly introduce the drawings required for the description of this application or the prior art. Obviously, the drawings in the following description are some embodiments of this application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0039] Figure 1 It is a real-time response diagram of recoverable high-sensitivity MNT (increase) / DNT (decrease) vapor fluorescence quenching;

[0040] Figure 2 (A) is the absorption spectrum of quantum dots (the solid line is for oil-soluble quantum dots, and the dashed line is for water-soluble quantum dots), Figure 2 (B) is the fluorescence spectrum of quantum dots (the solid line is for oil-soluble quantum dots, and the dashed line is for water-soluble quantum dots), Figure 2(C) are quantum dot photos with wavelengths of 550 nm, 580 nm, and 620 nm respectively. Under ultraviolet light irradiation, chloroform is in the lower layer and water is in the upper layer;

[0041] Figure 3 is a schematic diagram of the interaction between the fluorine-containing polymer aromatic ring and TNT;

[0042] Figure 4 is a schematic diagram of the interaction between the fluorosilicon of the fluorosilicon-containing polymer and TNT;

[0043] Figure 5 is a schematic diagram of the generation of free radicals by various mononitroalkylbenzenes;

[0044] Figure 6 is TM5-1 1 1H NMR: CDCl3 compound spectrum;

[0045] Figure 7 is TM5-2 1 1H NMR: CDCl3 compound spectrum;

[0046] Figure 8 is P1 1 1H NMR: CDCl3 compound spectrum;

[0047] Figure 9 is P2 1 1H NMR: CDCl3 compound spectrum;

[0048] Figure 10 is the GPC compound spectrum of P2;

[0049] Figure 11 is the solid ultraviolet absorption spectrum of the obtained polymer P1;

[0050] Figure 12 is the ultraviolet absorption spectrum of the obtained polymer P2;

[0051] Figure 13 is the fluorescence change diagram of the explosive MNT tested by P1;

[0052] Figure 14 is the fluorescence change diagram of the explosive TNT tested by P1;

[0053] Figure 15 is the fluorescence change diagram of the explosive DNT tested by P1;

[0054] Figure 16 is the image of stable operation with the increase of the instrument pumping time and air flow;

[0055] Figure 17 is the micro-test image of nitrotoluene (rising) and nitrobenzene (falling);

[0056] Figure 18 Test images of nitrotoluene (rising), dinitrotoluene (falling), and dinitrobenzene (falling);

[0057] Figure 19 Test images of polymethylnitrobenzene (rising), in large and trace amounts;

[0058] Figure 20 Test image of recoverable nitrotoluene (rising, second from the right) after testing TNT (falling, leftmost);

[0059] Figure 21 Test images without obvious interference from various liquid solvents and solids such as starch, sugar, wax, wall ash, and plant ash. Detailed implementation manners

[0060] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions in this application will be clearly and completely described below in conjunction with the accompanying drawings in this application. Obviously, the described embodiments are part of the embodiments of this application, rather than all of them. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of this application.

[0061] Unless otherwise specified, the experimental methods used in the embodiments of this application are all conventional methods. In the following embodiments, unless otherwise specified, all raw materials can be obtained through commercial purchase or conventional methods.

[0062] Monomer structure:

[0063] The structural formula of the first type of monomer is selected from one or more of the following:

[0064]

[0065] Among them, Y is Br or I. Among them, Y is Br or I. The general structural formula contains F at the ortho or meta position of Y in the benzene ring and may have N connected to an electron-withdrawing benzene ring (CF3 / NO2 / CN / F).

[0066] The structural formula of the second type of monomer is selected from one or more of the following:

[0067]

[0068] Among them, X is C or Si; R is an alkyl group C n H 2n+1 , where n is an integer within 1 - 25; Z is O, N, NH, or S. Specifically, when X is Si, the R it links to can be H.

[0069] The structural formula of the third type of monomer is selected from one or more of the following:

[0070]

[0071] Among them, X is C or Si; R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; Y is Br or I.

[0072] The structural formula of the fourth type of monomer is selected from one or more of the following:

[0073]

[0074] Among them, Y is Br or I; R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; the PEG chain has a structure containing multiple -OCH2CH2- repeating units.

[0075] The structural formula of the fifth type of monomer is selected from one or more of the following:

[0076]

[0077] Among them, R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; the PEG chain has a structure containing multiple -OCH2CH2- repeating units.

[0078] The structural formula of the fluorine-containing polymer is:

[0079]

[0080] Among them, X is C or Si; M is OR, NR2 or PEG, the PEG chain has a structure containing multiple -OCH2CH2- repeating units; when it is a non-spirofluorene structure, R is an alkyl C n H 2n+1 , alkenyl, alkynyl, fluorenyl or fluorene-based heterocyclic group, where n is an integer within 1 - 25; when X is Si, the R linked to it can be H, and the illustrated ring may or may not exist, and when it exists, it is fluorenyl.

[0081] It should be noted that: 1. The fluorine-containing first type of monomer is the core monomer; 2. a, b, c, d represent the number of different monomers linked to the reaction product; 3. X is C, Si, preferably Si, Z is O, N (depending on the valence bond, it can also be NH), S, preferably O, Y is Br, I, preferably I; 4. In particular, the PEG chain has a structure containing multiple -OCH2CH2- repeating units; 5. The above R is generally an alkyl (C n H 2n+1 ), where n is an integer within 1 - 25, in particular, when X is Si, the R linked to it can be H; 6. The above fifth type of monomer is prepared from the fourth type of monomer.

[0082] Typical molecules:

[0083] In order to demonstrate the differences between this class of polymers and other reported polymers, the following expands the two main types of polymer backbones so that researchers can further confirm the main structures intended to be protected by the present invention, specifically as follows:

[0084]

[0085] The above-expanded molecule M is OR, NR2, PEG. When it is a non-spirofluorene structure, R is an alkyl group (C n H 2n+1 ), alkenyl, alkynyl, or fluorenyl, fluorene-based heteroatom, where n is an integer within 1-25; when X is Si, the R it links can be H, and the illustrated ring may or may not exist. When it exists, it is fluorenyl.

[0086] It should be noted that the present invention emphasizes in the field of fluorescence detection of explosives, and the polymer has the following characteristics: one is a three-component or four-component polymer; the other is obtained by any permutation and combination of the above-mentioned species monomers, and it is always a copolymer of fluorenyl monomers, fluorine-containing monomers, and long-chain heteroatom aromatic monomers; in addition, the substituents of the molecules intended to be protected by the present invention include but are not limited to the above groups, and analog compounds caused by other groups also belong to the protection scope emphasized by the present invention.

[0087] Fluorescence detection principle:

[0088] 1. First, the electron-rich polymer xF-PPE-CP itself is a multi-conjugated compound (containing multiple benzene rings and triple bonds), forming π-electron delocalization, and having multiple alkoxy groups donating electrons, with strong fluorescence. Its absorption wavelength is 550-570 nm, and the excitation wavelength is 650-950 nm (wavelength red shift). In addition, due to the rigid backbones of terphenyl and spirofluorene silicon, by increasing the heteroatom nitrogen and oxygen chains, mutual stacking can be prevented, forming a rod-like stacked structure, weakening its aggregation-induced fluorescence quenching (ACQ), and meeting the basic conditions for fluorescence detection.

[0089] 2. Second, the doped CdSe / ZnS quantum dots have adjustable wavelengths and strong fluorescence, which can be adjusted in the range of 550-620 nm and wider, facilitating the adjustment of the absorption and excitation wavelengths of the polymer. Moreover, the CdSe / ZnS quantum dots have nanometer properties. As the mother nucleus, the polymer can be dispersed around it to form a nanofiber structure, thereby helping the testing of nitroaromatics. The quantum dots themselves also have a certain interaction with nitroaromatic vapors and can produce a fluorescence quenching reaction. Figure 2 (A) is the absorption spectrum of the quantum dots (the solid line is the oil-soluble quantum dots, and the dotted line is the water-soluble quantum dots), Figure 2(B) is the fluorescence spectrum of quantum dots (the solid line represents oil-soluble quantum dots, and the dashed line represents water-soluble quantum dots). Figure 2 (C) are photos of quantum dots with wavelengths of 550 nm, 580 nm, and 620 nm respectively. Under ultraviolet light irradiation, chloroform is in the lower layer and water is in the upper layer.

[0090] 3. Since the polymer structure has an electron-donating polyoxy side chain, while nitroaromatic hydrocarbons (polynitroaromatic compounds) are electron-deficient themselves and can evaporate under high-temperature heating. Due to van der Waals forces and π-π interactions, they can complex with each other, generate donor-acceptor bonds, weaken their electron density, and change the fluorescence emission intensity of xF-PPE-CP, thus achieving detection. For example, trinitrotoluene (TNT) has three nitro groups and can be complexed and recognized by electron-rich molecules. Figure 3 It is a schematic diagram of the interaction between the fluorinated polymer aromatic ring and TNT.

[0091]

[0092] 4. Particularly, silicon or fluorine atoms in some structures have weak interactions with nitro groups, which can increase the probability and intensity of polymer fluorescence changes (William C. Trogler: Chem. Commun., 2005, 5465 - 5467; Chem. Mater., 2007, 19, 6459–6470; J. Mater. Chem., 2008, 18, 3143 - 3156; Chem. Commun., 2010, 46, 6804 - 6806; J. Mater. Chem., 2012, 22, 2908 - 2914). Figure 4 It is a schematic diagram of the interaction between the fluorosilicon of the fluorinated silicon polymer and TNT.

[0093] 5. Due to the fluorene mother nucleus skeleton and polyether or amino chains among polymers, they are arranged to form a topological structure, avoiding aggregation-caused fluorescence quenching (ACQ), so as to form a gas path channel to facilitate the entry of explosive molecules and restrict the entry of other non-conforming molecules (too large in volume).

[0094] 6. This detection reaction also utilizes the molecular wire fluorescence amplification effect (quenching amplification effect - AFP). It is called the "molecular wire" effect or the "one-point contact, multi-point response" effect: its fluorescence enhancement and fluorescence quenching can be amplified, resulting in a multiple increase in sensitivity.

[0095] 7. Due to energy level matching and the particularity of nitroalkylbenzenes, various alkylbenzenes can form benzyl or other free radicals under ultraviolet light, which may lead to fluorescence enhancement. Figure 5 It is a schematic diagram of the generation of free radicals by various mononitroalkylbenzenes.

[0096] Raw material sources and detection methods:

[0097] 1. A small portion of the monomer raw materials are outsourced and customized by reagent companies or are directly commercially available, and the others are synthesized by ourselves. See the examples; the trinitrobenzene (TNB), trinitrotoluene (TNT), and dinitrotoluene (DNT) tested are all from commercially available standard concentration substances, and the others such as dinitrobenzene (DNB), nitrotoluene (MNT), nitrobenzene (NB), nitroethylbenzene (ENB), dimethylnitrobenzene (di-MNT), polymethylnitrobenzene, isopropylnitrobenzene (i-PNB), and tert-butylnitrobenzene (t-BNB) are commercially pure products.

[0098] 2. In the CDCl3 solution, the room temperature 1 1H NMR, 13 13C NMR, and 19 19F NMR spectra were recorded using a Varian liquid nuclear magnetic resonance spectrometer (400 MHz) from Westlake University, a partner. The chemical shifts were referenced to the residual protonated solvent. The 1H NMR spectrum was recorded using TMS (δ = 0.00 ppm) as an internal reference; the 13C NMR spectrum and 1 19F NMR spectrum were recorded using Acetone-d6 / CD2Cl2 / CDCl3 / DMSO-d6 as internal references. 13 13C NMR spectrum, 19 19F NMR spectrum. 1 1H NMR, 13 13C NMR, and 19 19F NMR peak type abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad peak.

[0099] 3. The polymer was tested using an Agilent GPC to measure the molecular weight (M w , M n , M z ) and the polydispersity index (PDI) of the polymer, and a Varian liquid high-temperature nuclear magnetic resonance spectrometer (400 MHz) was used for high-temperature 1H NMR testing of the polymer.

[0100] 4. The chemical-related parts of other parts not described in detail in the present invention are all conventional technical contents.

[0101] Total synthesis route: The polymer was synthesized by the linear method, and the monomers were synthesized by the divergent method and the convergent method. Below, in combination with the accompanying drawings, the preferred embodiments of the present invention are given and described in detail in conjunction with the experimental operation steps. First, different monomers were synthesized, and then the monomers were polymerized multiple times (in different orders) to obtain the required three (multi)-component polymers. By controlling the monomers, the catalyst ligands, and the amount of the cocatalyst, and then controlling the time and temperature, polymers with different molecular weights and different structures can be synthesized. The structures and linear synthesis routes of Polymers 1 and 2 are shown below:

[0102]

[0103] Implementation process of some typical molecules:

[0104] First part: Schematic illustration of monomer preparation

[0105] As the core part of the polymer backbone of the present invention - the first type of monomers and their analogs, the following can all be directly commercially purchased at a relatively low price. The commercially available first type of monomers are schematically shown as follows:

[0106]

[0107] While other similar monomers need to be outsourced for customization or synthesized by oneself. The following elaborates on the key synthesis steps of the synthesis and polymerization of the key monomers, the first type and the third type of monomers:

[0108] Typical implementation process of monomer synthesis:

[0109] Synthesis of the first type of monomers:

[0110] 1. Synthesis of compound TM1:

[0111]

[0112] General method:

[0113] Step 1: Take a 200 mL three-necked flask, connect the middle to a reflux condenser, add a tap at the top to a double manifold, add vacuum glass stoppers to both openings, and under nitrogen protection at 0 °C, add potassium ethoxide in ethanol solution (8 g, 95 mmol, 40 mL ethanol), stir continuously and cool, and slowly add o-nitro-p-fluoroaniline (SM1, 10 g, 64 mmol). Then slowly dropwise add 20 mL of pre-prepared 10% potassium hypochlorite (aq). After the bleach potassium hypochlorite solution is completely added, continue to stir the mixture for 30 min (to ensure complete reaction), filter, and wash the filter cake with a large amount of water. The residue is purified by silica gel with PE:DCM = 1:1 to obtain a bright yellow solid with a unique aromatic odor: 5-fluoro-benzo[c][1,2,5]oxadiazole-1-oxide - IM1 (8.05 g, 81%).

[0114] Step 2: Dissolve the product IM1 (50 mmol) from Step 1 in 40 mL of THF, stir and degas by bubbling nitrogen for about 30 minutes. Subsequently, slowly add dropwise a solution of triethyl phosphite (20 mL, 2 mol) to the degassed solution. Stir the resulting mixture at 60 °C for 12 h. Observe that the color of the mixture gradually darkens. After monitoring the completion of the reaction by TLC, cool to room temperature and dilute with 200 mL of water. Extract the diluted mixture with hexane. Wash the organic layer with brine to remove residual impurities and dry over anhydrous Na2SO4. Rotate evaporate the solvent under reduced pressure to obtain an orange semi-solid substance. Purify the crude product by silica gel column (PE:DCM = 1:1) to finally obtain pure 5-fluorobenzo[c][1,2,5]oxadiazole TM1 (6.94 g, 90%).

[0115]

[0116] IM1, 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.43 (1H, br), 7.02 - 7.13 (2H, br); TM1, 1 1H NMR: (CDCl3, 400 MHz): δ 7.83 (1H, m), 7.34 (1H, d, J 7.0), 7.20 (1H, m). 19 19F NMR (Acetone-d6): δ = -104.7 (m, F-5) ppm. 13 13C NMR (Acetone-d6): δ = 164.7 (d, J = 256.0 Hz, C-5), 150.6, 148.6, 126.9, 120.5, 99.5 ppm。

[0117] 2. Synthesis of Compound 1F-A:

[0118]

[0119] General Method:

[0120] Under an ice bath at 0 °C, a 100 mL single-necked flask was selected, TM1 (1.55 g, 11.2 mmol) was added, and it was dissolved with anhydrous dichloromethane (20 mL). Further, Br2 (2.69 g, 16.8 mmol, 1.5 eq, 1.2 mL) was slowly added dropwise thereto. After the addition was completed, the mixture was heated to reflux at about 60 °C. After about 12 h, the reaction was monitored by TLC to be completed. The reaction mixture was poured into ice water (100 mL) containing saturated Na2S2O3·5H2O, and stirred vigorously for 30 minutes. The resulting crude precipitate was collected and filtered, and the residue was eluted with silica gel column chromatography with PE:EA = 2:1. Finally, the pure product 1F-A (2.89 g, 87%) was obtained.

[0121]

[0122] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.56 (d, J = 8.08, 1H); 13 13C NMR: (CD2Cl2, 100 MHz): δ (ppm) = δ 161.74, 159.16, 148.19, 127.84 (J = 34.34), 110.51, 110.40, 92.17, 91.89; 19 19F NMR (CDCl3, 376 MHz): δ (ppm) = δ -98.66, -98.68.

[0123] 3. Synthesis of compound TM2:

[0124]

[0125] General method:

[0126] Step 1: A 250 mL three-necked flask was taken, connected to a reflux condenser and a double-tube, and a glass stopper was added to the side port. Under nitrogen protection, at 0 °C, an alcoholic solution of potassium ethoxide (8.4 g, 100 mmol, 50 mL ethanol) was added, and the mixture was continuously stirred and cooled. o-Nitro-4,5-difluoroaniline (SM2, 12.5 g, 72 mmol) was slowly added. Subsequently, 30 mL of a pre-prepared aqueous solution containing 6% potassium hypochlorite was slowly added dropwise. After the addition was complete, the mixture was stirred for an additional 40 minutes (to ensure complete reaction), then the mixture was filtered, and the filter cake was washed with a large amount of water. The residue was chromatographically separated on silica gel with PE:DCM = 1:1 to finally obtain a bright yellow solid: 5,6-difluorobenzo[c][1,2,5]oxadiazole-1-oxide-IM2 (10.53 g, 85%).

[0127] Step 2: Dissolve the product IM1 (40 mmol) obtained in Step 1 in 40 mL of THF, stir and degas with nitrogen bubbling for about 30 minutes. Subsequently, slowly add a solution of triethyl phosphite (30 mL, 3 mol) to the degassed solution. Stir the resulting mixture at 60 °C for 12 hours. Observe that the color of the mixture gradually darkens. After monitoring the reaction completion by TLC, dilute it with 250 mL of water at room temperature. Extract the diluted mixture with hexane. Wash the organic layer with brine to remove residual impurities, and dry it over anhydrous Na2SO4. Evaporate the solvent under reduced pressure to obtain an orange semi-solid substance. Purify the crude product by silica gel column (PE:DCM = 1:1) to finally obtain pure 5,6-difluorobenzo[c][1,2,5]oxadiazole TM2 (5.98 g, 87%).

[0128]

[0129] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.60 (t, J = 7.6 Hz, 2H); 13 13C NMR (CDCl3, 100 MHz): δ (ppm) = 154.6 (dd, J = 266, 21.7 Hz), 146.1 (t, J = 5.5 Hz), 101.2 (m). 19 19F NMR (CDCl3, 376 MHz): δ (ppm) = 121.03 (t, J = 7.5 Hz, 2F).

[0130] 4. Synthesis of Compound 2F-A:

[0131]

[0132] General Method:

[0133] Under an ice bath at 0 °C, select a 100 mL single-necked flask, add TM2 (4.99 g, 32 mmol), and dissolve it with anhydrous DCE. Take dibromohydantoin (10.98 g, 38.4 mmol, 1.2 eq), and slowly add it thereto. After completion, heat it to reflux at about 90 °C. After about 6 h, pour it into ice water containing saturated Na2S2O3·5H2O, stir vigorously for 30 minutes, collect and filter the crude precipitate, and elute it with silica gel column chromatography PE:EA = 1:1 to finally obtain the pure product 2F-A (9.24 g, 82%).

[0134]

[0135] 1313C NMR (CDCl3, 100 MHz): δ (ppm) = 152.5 (dd, J = 267, 22.7 Hz), 146.0 (t, J = 2.1 Hz), 94.0 (dd, J = 17.6, 8.9 Hz); 19 19F NMR (CDCl3, 376 MHz): δ (ppm) = -114.14 (s, 2F).

[0136] 5. Synthesis of compound TM3:

[0137]

[0138] General method:

[0139] Under stirring at room temperature (RT), 4-fluoro-1,2-phenylenediamine (5 g, 40 mmol) and anhydrous K2CO3 (6.2 g, 45 mmol) were added to a 250 mL single-necked glass bottle, and 100 mL of anhydrous DCM was measured and suspended for dissolution. Then, a solution of bromine (9.59 g, 60 mmol, 1.5 eq) in anhydrous DCM (30 mL, 2 M) was added dropwise to the solution, and the reaction was carried out at room temperature for 24 h. After monitoring the completion of the reaction by TLC, the excess bromine vapor was blown away with nitrogen, and the mixture was poured into ice water saturated with Na2S2O3·5H2O. The crude compound was extracted with dichloromethane and evaporated to dryness to obtain a red solid. The product TM3 (10.221 g, 90%) was finally obtained using column chromatography with PE:DCM = 1:2.

[0140]

[0141] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = 6.81 (d, 1H, J = 8 Hz), 3.63 (s, 4H). 13 13C NMR: (400 MHz, CDCl3): δ (ppm) = 154.16, 152.25, 135.75, 135.73, 128.73, 128.71, 109.44, 109.35, 108.83, 108.62, 96.78, 96.58. Anal. Calcd for (C6H5Br2FN2) (%): C 25.38, H 1.78, N 9.87. Found (%): C 24.29, H 1.83, N 10.14.

[0142] 6. Synthesis of compound 1F-B:

[0143]

[0144] General method:

[0145] Under nitrogen protection, a three-necked flask was used. Two necks were fitted with hollow glass stoppers, and a reflux condenser was connected in the middle with a tap. Then, compound TM2 (5.1 g, 18.05 mmol) was dissolved in 30 mL of ethanol solution and heated to reflux with stirring. A 20 mL aqueous solution of SeO2 (2.01 g, 18.1 mmol) was slowly added dropwise to the above reaction solution. The resulting reaction mixture was refluxed overnight to obtain a light brown solution with a yellow precipitate. The reaction was cooled to room temperature, the precipitate was filtered, washed with 5 × 100 mL of ethanol, and dried to obtain the powdered product 1F-B (5.5 g, 85%).

[0146]

[0147] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.75 (d, 1H); 19 19F NMR: (CDCl3, 376 MHz): δ (ppm) = δ -102 (d, 1F, J = 6.8); HRMS (ESI, m / z): C6HBr2FN2Se (M + H) + , Calculate: 359.76352; Find: 359.7637.

[0148] 7. Synthesis of compound TM4:

[0149]

[0150] General method:

[0151] A 100 mL single-necked flask was selected, and SM4 (6 g, 41.2 mmol) and anhydrous potassium carbonate (23.01 g, 166.5 mmol, 4 eq.) were added. A total of 50 mL of chlorobenzene was added. Bromine (16.46 g, 5.28 mL, 103 mmol, 5 eq.) pre-mixed with 10 mL of chlorobenzene was slowly added dropwise thereto with stirring. After completion, the temperature was raised to about 80 °C. After about 6 h, the reaction mixture was poured into ice water containing saturated Na2S2O3·5H2O. After vigorous stirring for 20 minutes, the resulting crude precipitate was collected and filtered. The pure product TM4 (8.95 g, 72%) was finally obtained by elution using silica gel column chromatography with PE:DCM = 1:2.

[0152]

[0153] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 3.68 (s, 4H); 1313C NMR (CDCl3, 125 MHz): δ (ppm) = δ 142.87 (d, J = 18.2), 140.95 (d, J = 18.2), 98.34 (dd, J = 12.6, 9.7); 19 19F NMR (CDCl3, 376 MHz): δ (ppm) = δ -139.06; HRMS (ESI, m / z): calcd for C6H5N2Br2F2 [M+H] + : 302.8756, Found: 302.8762.

[0154] Synthesis of Compound 2F-B:

[0155]

[0156] General method:

[0157] Under nitrogen protection, take a 100 mL three-necked flask, seal the side port with a hollow glass stopper, connect a reflux condenser to the middle port and add a tap, then dissolve Compound TM2 (3.2 g, 10.60 mmol) in 20 mL of ethanol solution under stirring and heat to reflux. Slowly add a 20 mL hot aqueous solution of SeO2 (1.22 g, 11.0 mmol) dropwise to the above reaction solution. Reflux the resulting reaction mixture overnight to obtain a light brown solution with a yellow precipitate. Cool the reaction to room temperature, extract three times with ethyl acetate, dry the organic phase with anhydrous sodium sulfate, evaporate and concentrate under vacuum, and purify the product by silica gel column chromatography (PE:DCM = 5:1) to obtain a pale yellow solid 2F-B (3.315 g, 83%).

[0158]

[0159] 13 13C NMR: (CDCl3, 100 MHz): δ (ppm) = δ 152.08, 149.94 (d, J = 22.68), 100.52 (dd, J = 15.12, 7.56); 19 19F NMR: (DMSO-d6, 376 MHz): δ (ppm) = δ -121.65; HRMS (ESI, m / z): calcd for C6HN2Br2F2Se [M+H] + : 376.7624, Found: 376.7634.

[0160] Synthesis of the third type of monomer:

[0161] 9. Synthesis of Compound 2F-D:

[0162]

[0163] SM5-1: R, R = CH3, CH3;

[0164] SM5-2:

[0165] General method:

[0166] Pre-treat trimethylsilylacetylene (2.5 eq.) under nitrogen protection for deoxygenation, and then dissolve SM5 (1 eq.) in a 100 mL single-neck flask equipped with a magnetic stirrer and a reflux condenser. Under nitrogen protection at room temperature, add 50 mL of anhydrous toluene, add Pd(PPh3)2Cl2 (10%) and CuI (5%), and then add 20 mL of diethylamine (Tol. / Et2NH = 5:2). Slowly drop the previously deoxygenated trimethylsilylacetylene solution into this solution, then heat the mixed solution to 110 °C and stir at this temperature for 12 hours. After the reaction is completed, remove the solvent by vacuum evaporation. Extract three times with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, concentrate again, and elute the crude product on a silica gel column with n-Hex:EA = 8:1 to obtain the yellow solid compound IM5.

[0167]

[0168] Other R groups can be synthesized by following the above synthetic method, only need to adjust the TMS mono-protected alkyne equivalent / catalyst for synthesis.

[0169] The first type: R, R = CH3, CH3

[0170]

[0171] 1 H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.61 (dd, J = 7.9, 0.7, 2H), 7.5 (dd, J = 1.5, 0.7, 2H), 7.45 (dd, J = 7.9, 1.4, 2H), 1.45 (s, 6H), 0.27 (s, 18H); 13 C NMR: (CDCl3, 100 MHz): δ (ppm) = δ 153.8, 138.8, 131.2, 126.3, 122.0, 120.1, 105.8, 94.5, 46.9, 26.8, 0.0; HRMS(ESI) calculated for C 25 H 31 Si2[M + H] + : 387.1964, found: 387.1963.

[0172] The second type:

[0173]

[0174] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.93 (d, J = 7.4, 1H), 7.83 (d, Jm = 7.8, 1H), 7.58 (d, J = 7.8, 1H), 7.45 (t, J = 7.3, 1H), 7.19 (t, J = 7.3, 1H), 6.95 (s, 1H), 6.79 (d, J = 7.4, 1H), 0.24 (s, 9H); 13 13C NMR: (CDCl3, 100 MHz): δ (ppm) = δ 149.2, 147.7, 141.9, 141.4, 132.1, 128.2, 128.1, 127.8, 124.3, 122.9, 120.28, 120.27, 105.4, 95.0, 65.7, 0.1; MS (MALDI-TOF): calcd. for C 35 H 32 Si2([M] + ): 508.204, found: 507.473.

[0175] Synthesis of Compound 2F-D:

[0176]

[0177] IM5-1: R, R = CH3, CH3;

[0178] IM5-2:

[0179] General method:

[0180] In a 200 mL single-necked flask, dissolve Compound IM5 (1 eq.) in a mixed solution of 50 mL of tetrahydrofuran (THF) and 50 mL of methanol (MeOH), i.e., THF:MeOH = 1:1. Then add anhydrous potassium carbonate (10 eq.). Stir the mixture at room temperature for 12 hours and monitor the reaction progress by thin-layer chromatography (TLC) (PE:DCM = 4:1). After the reaction is completed, filter the resulting solid and wash it continuously with water until the solution is neutral. Finally, perform column chromatography separation on the filtered residue (PE:DCM = 6:1) to obtain white solid TM5 (76%).

[0181]

[0182] The synthesis methods for other R groups are the same, only need to adjust the base equivalent for synthesis.

[0183] TM5-1: R, R = CH3, CH3.

[0184]

[0185] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.86 (d, J = 7.6, 1H), 7.80 (d, J = 7.9, 1H), 7.53 (d, J = 7.9, 1H), 7.40 (t, J = 7.5, 1H), 7.14 (t, J = 7.5, 1H), 6.89 (s, 1H), 6.73 (d, J = 7.6, 1H), 2.98 (s, 1H); 13 13C NMR: (CDCl3, 100 MHz): δ (ppm) = δ 149.4, 147.6, 141.9, 141.6, 132.2, 128.2, 128.1, 128.0, 124.2, 121.9, 120.4, 120.3, 83.9, 77.9, 65.7; MS (MALDI-TOF) calc. mass for C 29 H 16 ([M] + ): 364.125, found: 363.221. Figure 6 for TM5-1 1 1H NMR: CDCl3 compound spectrum.

[0186] TM5-2:

[0187]

[0188] 1 1H NMR: (CDCl3, 400 MHz): δ (ppm) = δ 7.65 (dd, J = 7.8, 0.7 Hz, 2H), 7.56 (dd, J = 1.5, 0.7 Hz, 2H), 7.49 (dd, J = 7.8, 1.4 Hz, 2H), 3.14 (s, 2H), 1.47 (s, 6H); 13 13C NMR: (CDCl3, 100 MHz): δ (ppm) = δ 153.8, 139.0, 131.4, 126.5, 121.1, 120.2, 84.3, 77.4, 346.9, 26.8; HRMS: C 54 H 102 I2N2 (M + H) + , calculated for C 19 H 15 [M + H] +:243.1169,found:243.1168. Figure 7 For TM5-2 1 H NMR: CDCl3 compound spectrum.

[0189] Part II: Schematic diagram of polymer synthesis

[0190] 11. Synthesis of compound P1:

[0191]

[0192] X=C, R=CH3,R'=C 14 H 29 , the key first class monomers containing sulfur and difluoride are commercially available.

[0193] General approach:

[0194] Pre- i Pr2NH:Tol.=2:8) was placed in a 100mL Shrek reaction bottle that was dried and filled with nitrogen. Nitrogen was bubbled to remove oxygen. Under nitrogen protection, TM5-1 (189mg, 0.78mmol), 4,7-dibromo-5,6-difluorobenzo[c][1,2,5]thiadiazole (A, 257mg, 0.78mmol), Pd(PPh3)4 (90mg, 0.078mmol) and CuI (13mg, 0.070mmol) were placed in a 100mL single-necked flask. The flask was degassed and backfilled with nitrogen three times, and 30mL of oxygen-free solvent ( i Pr2NH:Tol.=2:8). The mixture was heated at 65°C for 1 day. While hot and under the protection of high-pressure nitrogen flow, Pd(PPh3)4 (90 mg, 0.078 mmol) and 1,4-diiodo-2,3-di(n-tetradecyloxy)benzene (B, 588.6 mg, 0.78 mmol) were weighed and quickly added. The mixture was heated at 65°C for another 2 days, cooled to room temperature, and the solvent was removed. The solid was dissolved in dichloromethane, washed with aqueous ammonium chloride to remove copper ions, and dried with Na2SO4. The solvent was removed in vacuo, and the residue was reprecipitated from dichloromethane into methanol, and the dissolution and precipitation were repeated many times. The yellow powder solid was collected by filtration to obtain polymer P1 (677 mg, 73%).

[0195]

[0196] X=C, R=CH3,R'=C 14 H 29 , P1: 1 H NMR: (CDCl3, 400MHz): see Figure 8 ;

[0197] 12. Synthesis of Compound P2:

[0198]

[0199] X = C, R' = C 14 H 29 , and the key first - type monomer containing sulfur and difluoro is commercially available.

[0200] General method:

[0201] Pre - place 40 mL of solvent ( i Pr2NH:Tol. = 2:8) into a dry and nitrogen - filled 100 mL Schlenk reaction flask. Remove oxygen by nitrogen bubbling. Under nitrogen protection, charge TM5 - 2 (284 mg, 0.78 mmol), 4,7 - dibromo - 5,6 - difluorobenzo[c][1,2,5]thiadiazole (A, 257 mg, 0.78 mmol), Pd(PPh3)4 (90 mg, 0.078 mmol) and CuI (13 mg, 0.070 mmol) into a 100 mL single - necked flask. Degas the flask and back - fill with nitrogen 3 times, and then add 30 mL of oxygen - free solvent ( i Pr2NH:Tol. = 2:8) under nitrogen atmosphere. Heat the mixture at 65 °C for 1 day, cool to room temperature, and remove the solvent. Dissolve the solid in dichloromethane, wash with aqueous ammonium chloride solution to remove copper ions, and dry with Na2SO4. Remove the solvent under vacuum, redissolve the residue in anhydrous toluene, weigh and quickly add Pd(PPh3)4 (90 mg, 0.078 mmol), add 2,7 - diborate - 9,9'-spirobifluorene (B, 443 mg, 0.78 mmol). Heat the mixture at 110 °C for 1 day. While hot and under the protection of a high - pressure nitrogen stream, weigh and quickly add Pd(PPh3)4 (90 mg, 0.078 mmol), 1,4 - diiodo - 2,3 - bis(n - tetradecyloxy)benzene (C, 588.6 mg, 0.78 mmol). Heat the mixture at 110 °C for another 1 day, cool to room temperature, and remove the solvent. Dissolve the solid in dichloromethane, wash with aqueous ammonium chloride solution to remove copper ions, and dry with Na2SO4. Remove the solvent under vacuum, reprecipitate the residue from dichloromethane into methanol, and repeat the dissolution and precipitation several times. Collect the yellow powder solid by filtration to obtain polymer P2 (943 mg, 83%).

[0202]

[0203] X = C, R' = C 14 H29 , P2: 1 1H NMR: (CDCl3, 400 MHz): See Figure 9 ; GPC: M w , M n See Figure 10 .

[0204] Part III: Schematic Diagram of Quantum Dot Doping

[0205] The synthesis can be carried out with reference to Nano Letters, 2001, 1(4), 207 - 211 and Nanoscale Res Lett 1, 2006, 620. CdSe / ZnS quantum dots with wavelengths (550 nm - 620 nm) such as 550 nm, 580 nm, and 620 nm can be customized, and the oil phase and water phase can be controlled. Here, it is preferably synthesized into the oil phase as much as possible. Note that it must be shaken well before use.

[0206] Weigh P1 or P2 and prepare a 5 mg / mL dichloromethane solution. Take 1 mL of the above solution and slowly add 1 mL of 5 mg / mL CdSe / ZnS quantum dots with an oil phase of 550 nm under stirring. Then, ultrasonically vibrate it for about 10 min. Further concentrate the solution using a rotary evaporator (under vacuum at 40 °C) until it becomes a viscous solid. Dilute it again to a 10 mL dichloromethane solution, and then it is ready for doping.

[0207] Fluorescence test data:

[0208] 1. UV absorption of xF - PPE - CP solid P1: The UV absorption spectrum of the obtained polymer P1 solid is as Figure 11 shown.

[0209] 2. According to the test results, select P2, dissolve it in dichloromethane, spin - coat it on an acrylic substrate at 1 mg / mL, and perform fluorescence - related tests with the best absorption wavelength of 550 - 600 nm. The UV absorption spectrum of the obtained polymer P2 solid is as Figure 12 shown.

[0210] 3. P2, spin - coated on an acrylic substrate at 1 mg / mL, under the excitation wavelength of 570 nm and heating conditions (100 °C), the test results of the explosives MNT and DNT being contaminated / non - contaminated: The fluorescence change of the explosive MNT tested by P1 is as Figure 13 shown; The fluorescence change of the explosive TNT tested by P1 is as Figure 14 shown; The fluorescence change of the explosive DNT tested by P1 is as Figure 15 shown.

[0211] Note: exc_x nm represents the test at x nm under the heating condition (100°C), and exc_x nm_y s represents the test of exposing to explosives for y s under the heating condition (100°C). For example, exc_570nm refers to the test at 570 nm under the heating condition (100°C), and the excitation is carried out by spin-coating at a concentration of 1 mg / mL, and so on; exc_570nm_5s refers to the test of exposing to explosives for 5 s at 570 nm under the heating condition (100°C), and the excitation is still carried out by spin-coating at a concentration of 1 mg / mL, and so on.

[0212] Explosive response data:

[0213] Test method:

[0214] 1. Solution preparation: Using chloroform as the solvent, weigh about 20 mg of xF-PPE-CP (P2) to prepare a 2 mg / mL solution of xF-PPE-CP (P2) with a total volume of 10 mL.

[0215] 2. Preparation of thin film by drop casting method: Drop about 0.2 mL of the 2 mg / mL solution of xF-PPE-CP (P2) onto the acrylic substrate, and then age it in an oven at 60°C for 1 h for later use.

[0216] 3. Preparation of thin film by spin coating method: Spin coat the G solution on a quartz wafer (Φ = 5 mm) using a spin coater at a speed of 1500 rpm / min for a total time of 5 s to form a thin film for use. It is also considered to spin coat it again for a total of two times.

[0217] 4. Test equipment: Use the test equipment and its auxiliary components described in the company's patents CN105866091A / CN201720381260.7 / CN214584899U.

[0218] 5. Measured results:

[0219] (1) Temperature dependence: Measure the fluorescence spectra at different temperatures. As the temperature increases, the fluorescence intensity of the thin film increases slightly and then slowly decays. When the internal cavity temperature is 70°C, the fluorescence intensity of the thin film decreases by 15%. Then it continues to slowly decrease and approaches the initial value, and then tends to be stable. This result proves that the thin film is stable to temperature and air.

[0220] (2) Standard test procedure: When testing various trace explosives, always use a micro syringe to take a solution of its standard concentration and place it on the sampling sheet, and then wait for it to volatilize for 10 s before further testing. When testing pure substances, directly smear the pure explosive at the bottle mouth and start testing. The response images of testing different types of explosives are specifically as Figures 16 - 21 shown.

[0221] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A fluorinated polymer of a specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer, characterized in that, The structural formula of the fluoropolymer is as follows: or Wherein, A is a third type of monomer or a fifth type of monomer, and both the third type of monomer and the fifth type of monomer are diyne monomers; B is a first type of monomer or a fourth type of monomer; C is a first type of monomer or a fourth type of monomer; E is a second type of monomer; F is a first type of monomer or a fourth type of monomer; a, b, c, and d represent the numbers of different monomers linked in the reaction product.

2. The fluoropolymer of the specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer according to claim 1, characterized in that, The structural formula of the first type of monomer is selected from one or more of the following: Wherein, Y is Br or I; the structural formulas all contain F at the ortho or meta position of the benzene ring Y, and may have N-linked electron-withdrawing benzene rings (CF3 / NO2 / CN / F).

3. The fluorine-containing polymer of the specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer according to claim 1, characterized in that, The structural formula of the second type of monomer is selected from one or more of the following: Wherein, X is C or Si; R is an alkyl C n H 2n+1 , wherein n is an integer within 1 - 25; Z is O, N, NH or S.

4. The fluoropolymer of the specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer according to claim 1, characterized in that The structural formula of the third type of monomer is selected from one or more of the following: Wherein, X is C or Si; R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; Y is Br or I.

5. The fluoropolymer of the specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer according to claim 1, characterized in that, The structural formula of the fourth type of monomer is selected from one or more of the following: wherein, Y is Br or I; R is an alkyl C n H 2n+1 , wherein n is an integer within 1 - 25; the PEG chain has a structure containing multiple -OCH2CH2- repeating units.

6. The fluorine-containing polymer of the specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer according to claim 1, characterized in that The structural formula of the fifth type of monomer is selected from one or more of the following: wherein, R is an alkyl C n H 2n+1 , where n is an integer within 1 - 25; the PEG chain has a structure containing multiple -OCH2CH2- repeating units.

7. The fluoropolymer of the specific mononitroalkylbenzene aromatic explosive tracer according to claim 1, characterized in that, The structural formula of the fluoropolymer is as follows: Wherein, X is C or Si; M is OR, NR2 or PEG, and the PEG chain has a structure containing multiple -OCH2CH2- repeating units; when it is a non-spiro fluorene structure, R is an alkyl C n H 2n+1 , alkenyl, alkynyl, fluorenyl or fluorenyl with a heteroatom, where n is an integer within 1 - 25; when X is Si, the R linked thereto can be H, and the illustrated ring may or may not exist, and when it exists, it is fluorenyl.

8. A method for preparing a fluorinated polymer of a specific mononitroalkylbenzene aromatic hydrocarbon explosive tracer according to any one of claims 1-7, characterized in that, It includes the following synthetic route:

9. Application of the fluoropolymer of the specific mononitroalkylbenzene aromatic explosive tracer described in any one of claims 1-7 in the field of explosive detection.

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