CN116284696A - Polyaryleneyne as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a polyarylenyne and its preparation method and application. It uses binary toluene acetylenic monomers, binary trimethylsilylacetylene monomers and monoaryl aryl iodide monomers as raw materials. In the presence of an organic ligand, a palladium catalyst, an acid-binding agent and a solvent, the polyarylene is obtained by polymerization. The present invention prepares polyarylenynes with good solubility and thermal stability through the above one-pot method. The reaction raw materials of this method are easy to obtain, the polymerization reaction is efficient and the substrate has wide applicability, and polyarylenes with novel structures can be prepared. Enyne; after the introduction of structural units with AIE properties, polyarylenynes can be endowed with AIE characteristics, which can be used to detect nitroaromatic explosives and trivalent ruthenium ions, in chemical sensors, responsive materials, photolithographic patterning and biological Imaging and other fields have good application prospects.

Description

A kind of polyarylene and its preparation method and application

technical field

The invention relates to the fields of polymer synthesis and material science, in particular to a polyarylene and its preparation method and application.

Background technique

The use of new polymerization reactions to prepare polymer materials with new structures has important research significance and application value. Polymerization reactions involving alkyne monomers can prepare polymers containing unsaturated double bonds or triple bonds, which in turn can be used to construct functional polymer materials. The multi-component polymerization involving non-activated internal alkynes has the advantages of simple operation, high conversion rate, less by-products, and mild conditions. It is a powerful means to synthesize polymer functional materials with complex structures and conjugated backbones. However, there are few reports in this area. In 2016, Tang Benzhong's research group used palladium acetate and sodium carbonate to catalyze the three-component polymerization reaction of binary internal alkyne, dibromoarene and potassium ferrocyanide to prepare high molecular weight polyaryl acrylonitrile (Macromolecules2016, 49, 8888 ). Subsequently, they reported the nickel-catalyzed three-component polymerization reaction of dihaloarene, binary internal alkyne and Grignard reagent for in situ construction of polyarylene with high molecular weight (Polym.Chem.2020, 11, 5601 ).

Traditional luminescent materials emit light in solution, but do not emit light in the aggregated state, that is, fluorescence quenching, which is due to the increase of non-radiative transitions due to intermolecular interactions, resulting in weakened fluorescence. In 2001, Tang Benzhong's research group discovered for the first time that some compounds do not emit light in solution, but emit light in an aggregated state. This kind of abnormal photophysical phenomenon is named aggregation-induced emission (Aggregation-induced emission, AIE), which is mainly It is due to the restricted rotation in the aggregated state molecules, which reduces the attenuation of non-radiative energy. Due to their unique photophysical properties, this kind of luminescent molecules do not emit light or emit weak light in the solution, but the luminescence is enhanced in the aggregated state, which solves the long-standing problem of fluorescence quenching of luminescent materials. In recent years, AIE materials have become a research hotspot and have been widely used in fluorescent chemical sensors, organic light-emitting diodes, multiple responsive materials, photolithography patterning, biological imaging and other fields. Compared with organic small molecule materials, polymer materials often have better processing properties and are easier to prepare large-area devices. Therefore, the preparation of AIE active polymer materials with new structures based on novel polymerization reactions has important application value.

Contents of the invention

The technical problem to be solved by the present invention is to provide a kind of polyaryl enyne and its preparation method and application. The body is used as a raw material, reacted in the presence of an organic ligand, a palladium catalyst, an acid-binding agent and a solvent, and can be polymerized to obtain a polyarylene with a conjugated skeleton. This kind of polyarylenyne has good solubility and thermal stability. The polyarylenyne prepared after introducing structural units with AIE properties can be used to detect nitroaromatic explosives and trivalent ruthenium ions. It has good application prospects in the fields of sensors, multiple response materials, photolithographic patterning, and biological imaging.

In order to solve the above technical problems, the present invention provides the following technical solutions:

The first aspect of the present invention provides a polyarylenyne, the polyarylenyne has the following general structural formula:

Wherein, x and y are respectively selected from any integer ranging from 2 to 200;

R and R' are respectively selected from any group shown in formula 1 to formula 22, and R" is selected from any group shown in formula 23 to formula 27;

The structures of the groups represented by the above formulas 1 to 27 are as follows:

Wherein, m is selected from any integer ranging from 1 to 18.

The second aspect of the present invention provides a method for preparing the polyarylenyne described in the first aspect. Under an inert atmosphere, the binary tolan monomer shown in formula (I), the formula (II) The shown binary trimethylsilylacetylene monomer reacts with the monoaryl aryl iodide monomer shown in formula (III) in the presence of an organic ligand, a palladium catalyst, an acid-binding agent and a solvent to obtain the polyarylene alkenyne;

The structures of the compounds shown in the above formulas (I) to (III) are as follows:

Further, the binary toluene monomer is prepared by Sonogashira reaction between phenylacetylene and a binary halogenated aromatic compound, the binary halogenated aromatic compound is X-R-X, and X is bromine or iodine.

In some preferred embodiments, under an inert atmosphere, add binary halogenated aromatic compounds, triphenylphosphine, bistriphenylphosphine palladium dichloride, and cuprous iodide to the solvent, and then add Phenylacetylene is reacted at 25-80° C. for 12-36 hours to obtain the binary toluene monomer.

In some preferred embodiments, the solvent is a mixed solvent obtained by mixing triethylamine and tetrahydrofuran at a volume ratio of 4:1.

Further, the binary trimethylsilylacetylene monomer is prepared by Sonogashira reaction between trimethylsilylacetylene and a binary halogenated aromatic compound, the binary halogenated aromatic compound is X-R-X, X is bromine or iodine.

In some preferred implementations, under an inert atmosphere, add binary halogenated aromatic compounds, triphenylphosphine, bistriphenylphosphine palladium dichloride, and cuprous iodide to the solvent, and then add three Methylsilylacetylene is reacted at 25-80°C for 12-36 hours to obtain the binary trimethylsilylacetylene monomer.

In some preferred embodiments, the solvent is a mixed solvent obtained by mixing triethylamine and tetrahydrofuran at a volume ratio of 4:1.

Further, the organic ligand is one or more of triphenylphosphine, tri-tert-butylphosphine, bis(2-diphenylphosphinephenyl) ether.

Further, the palladium catalyst is one or more of palladium acetate, palladium dichloride, and bis(triphenylphosphine)palladium dichloride.

Further, the acid-binding agent is one or more of potassium carbonate, sodium carbonate, and cesium carbonate.

Further, the molar ratio of the binary toluene monomer, the binary trimethylsilylacetylene monomer, the monoaryl iodide monomer, the organic ligand, the palladium catalyst and the acid-binding agent is 1: 1:2:0.15～0.3:0.025～0.2:2～4.

Further, the solvent (polymerization reaction) is a mixed solvent of a polar aprotic solvent and methanol, and the polar aprotic solvent is N, N-dimethylformamide and/or N, N dimethylacetamide .

Further, the volume ratio of the polar aprotic solvent to methanol in the solvent (polymerization reaction) is preferably 100-300:1, more preferably 150-200:1.

Further, the molar ratio of the reactive monomer to the solvent is preferably 0.05-0.25 mol:1 L, more preferably 0.05-0.125 mol:1 L, and the reactive monomer refers to the sum of monomers in the reaction system.

Further, the temperature of the reaction (polymerization reaction) is preferably 60-150°C, more preferably 80-120°C; the reaction time is preferably 0.5-24h, more preferably 1-12h.

Further, the preparation method also includes a post-treatment process, specifically: adding chloroform to the reacted polymer solution to obtain a mixed solution, adding the mixed solution dropwise into methanol, and precipitating to obtain polyarylene.

The third aspect of the present invention provides an application of the polyarylenyne described in the first aspect in the detection of polynitroaromatic compounds and/or Ru3 ⁺ , the polyarylenyne has a structure of AIE properties unit.

Further, the structural units with AIE properties include tetraphenylethylene structural units.

Compared with prior art, the beneficial effect of the present invention:

1. The present invention uses binary toluene monomers, binary trimethylsilylacetylene monomers and monoaryl aryl iodides as monomers to prepare polyarylenynes with novel structures. The above synthesis method can endow the prepared polymer with AIE characteristics after introducing the structural unit with AIE properties. In addition, the reaction raw materials of this synthesis method are easy to obtain, the synthesis efficiency is high, and the molecular weight of the polymer can be regulated by adjusting the process parameters, and the synthesis method has a wide range of substrate applicability and good functional group compatibility, and can introduce a variety of functions sexual group.

2. The polyarylene prepared by the present invention has good processability and can be dissolved in dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature In common organic solvents, and has good thermal stability, when heated to 352 ° C, the mass of the polymer only decreases by about 5%; in addition, the above-mentioned polyarylenynes exhibit excellent performance after introducing structural units with AIE properties. Its AIE performance can be used to detect nitroaromatic explosives and trivalent ruthenium ions, and has good application prospects in the fields of chemical sensors, multiple response materials, photolithographic patterning, and biological imaging.

Description of drawings

Fig. 1 is the structural representation of polyarylene;

Fig. 2 is the proton nuclear magnetic resonance spectrogram (* represents the solvent peak) of the polyarylenynes prepared in Example 1 and their corresponding monomers in _CDCl3 ;

Fig. 3 is the thermal weight loss curve of the polyarylenyne prepared in Example 1, the test condition: under nitrogen atmosphere, the heating rate is 10°C/min;

Fig. 4 is the AIE curve diagram of the polyarylene prepared by embodiment 7;

Fig. 5 is the fluorescence spectrogram that detects picric acid under polyarylenyne aggregation state prepared in embodiment 7;

Fig. 6 is a fluorescence spectrum diagram for detection of ruthenium (III) in the aggregated state of the polyarylenyne prepared in Example 7.

Detailed ways

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. "Include" or "comprising" in the present invention means that it may include or include other components in addition to the components mentioned. The "comprising" or "comprising" mentioned in the present invention can also be replaced by the closed "is" or "consisting of".

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and implement it, but the examples given are not intended to limit the present invention.

Example 1

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomers

Add 8.8g (40mmol) p-iodophenol, 1.6g (40mmol) sodium hydroxide and 0.4g (2.4mmol) potassium iodide to a 500mL double-necked round bottom flask equipped with a condensing device, vacuumize and fill with nitrogen for three times, and then use a syringe to 30 mL of water and 180 mL of ethanol were added to the flask, heated to 90°C, and 4.88 g (20 mmol) of 1,6-dibromohexane was added dropwise into the flask. After the dropwise addition, the reaction system continued to be heated to reflux for 24 hours. Then the reaction solution was cooled to room temperature, and after the ethanol was removed by rotary evaporation, it was diluted with dichloromethane, washed with a large amount of water three times, dried with anhydrous magnesium sulfate, filtered with suction, and the filtrate was spin-dried to obtain a crude product, which was separated and purified by column chromatography. , and dried in vacuo to obtain 7.34 g of white solid 1,6-bis(4-iodophenoxy)hexane (70.5% yield).

Add 5.22g (5mmol) 1,6-bis(4-iodophenoxy)hexane, 0.32g (1.2mmol) triphenylphosphine, 0.152g (0.8mmol) iodide in a 250mL double-necked round bottom flask Copper, 0.280g (0.4mmol) bistriphenylphosphine palladium dichloride, evacuated and filled with nitrogen three times. Add 30mL tetrahydrofuran and 120mL triethylamine and stir to dissolve, add 2.24g (12mmol) phenylacetylene to the reaction system in batches at room temperature, and stir overnight at room temperature. After washing with ethylamine, the filtrate was spin-dried to obtain a crude product, which was separated and purified by column chromatography, and vacuum-dried to constant weight to obtain 3.26 g (yield: 69.4%) of a light yellow solid, which is a binary toilene monomer. ¹ H NMR (300MHz, CDCl ₃ )δ7.72,7.53,7.50,7.48,7.45,7.37,7.34,7.32,7.30,6.88,6.85,4.01,3.99,3.97,1.88,1.86,1.84,1.81,1.79,1.54 ,1.53.

(2) Preparation of binary trimethylsilylacetylene monomer

Add 5.56g (20mmol) of bisphenol A and 6.9g (50mmol) of potassium carbonate into a 250mL double-necked round bottom flask equipped with a condensing device, add 100mL of acetone and heat; then fully dissolve 11g (40mmol) of p-bromine with 50mL of acetone Benzyl bromide was added dropwise to the refluxed flask and refluxed overnight. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was spin-dried, diluted with 100 mL of dichloromethane, washed with a large amount of water, and the organic phase was dried with anhydrous magnesium sulfate and filtered with suction to obtain a crude product, which was separated and purified by column chromatography. Vacuum drying afforded 9.73 g of white solid 4,4'-(isopropyldiphenyl)-bis(4-bromo)ether (85.9% yield).

Add 5.64g (10mmol) 4,4'-(isopropyldiphenyl)-bis(4-bromo)ether, 0.315g (1.2mmol) triphenyl Phosphine, 0.152g (0.8mmol) of cuprous iodide, 0.281g (0.4mmol) of bistriphenylphosphinepalladium dichloride, evacuated and filled with nitrogen three times. Add 20mL tetrahydrofuran and 80mL triethylamine and stir to dissolve, then add 2.16g (22mmol) trimethylsilylacetylene in batches under heating at 80°C, react overnight, filter the reaction solution with diatomaceous earth after the reaction, and use Washed with triethylamine, the filtrate was spin-dried to obtain the crude product, which was separated and purified by column chromatography, and dried in vacuum to constant weight to obtain 5.27 g of white solid (yield rate 87%), which was binary trimethylsilylacetylene mono body. ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.50, 7.47, 7.38, 7.35, 7.16, 7.13, 6.88, 6.85, 5.04, 5.00, 1.65, 1.57, 0.27.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of binary toluene acetylenic monomers, 60.1 mg (0.1 mmol) of binary trimethylsilylethyne monomers, and monoaryl aryl iodides into a 10 mL polymerization tube with side arms. 46.8mg (0.2mmol) of monomer, 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 4 hours. After the reaction was completed and returned to room temperature, the reaction solution was diluted with 10 mL of chloroform, and the solution was added dropwise to 200 mL of vigorously stirred methanol through a dropper plugged with cotton. solution, allowed to stand, filtered, and dried to constant weight to obtain light yellow powder (90.7% yield). The results of gel permeation chromatography (GPC) showed that the weight average molecular weight (M _w ) was 17900, and the molecular weight distribution (PDI) was 2.45. ¹ H NMR (300MHz, CDCl ₃ )δ7.58,7.52,7.43,7.41,7.36,7.21,7.18,7.13,7.05,6.82,6.78,6.75,6.67,6.60,4.98,4.89,4.28,3.87,3.82,3.75 , 3.66, 3.60, 3.54, 1.70, 1.54.

The H NMR spectrum comparison of the polymer prepared in this example and its corresponding monomer is shown in Figure 2, where the resonance absorption peak of the binary trimethylsilylacetylene monomer at δ0.27 disappears in the polymer , and other NMR peaks in the monomer can be assigned in the polymer, which proves that the polymerization reaction occurs smoothly, and the polyarylenyne is successfully prepared.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties.

Fig. 3 is the thermogravimetric curve of the polyarylenyne prepared in this example. It can be seen from the figure that the material loses only 5% of its weight when heated to 352° C., indicating that it has good thermal stability.

Example 2

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer

Add 2.1g (5mmol) 4,4'-dibromotriphenylamine, 0.158g (0.6mmol) triphenylphosphine, 0.076g (0.4mmol) cuprous iodide, 0.140 g (0.2 mmol) of bistriphenylphosphine palladium dichloride, evacuated and filled with nitrogen three times. Add 20mL tetrahydrofuran and 80mL triethylamine and stir to dissolve, then add 1.18g (12mmol) trimethylsilylacetylene to the reaction flask in batches under the condition of heating at 80°C, stir and react overnight, and filter with diatomaceous earth after the reaction is completed. Washed with triethylamine, the filtrate was spin-dried to obtain a crude product, which was separated and purified by column chromatography, and vacuum-dried to constant weight to obtain 1.37 g of a light yellow solid (62.8% yield), which was dibasic trimethylsilyl Acetylene monomers. ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.34, 7.31, 7.27, 7.25, 7.11, 7.08, 7.05, 6.97, 6.94, 0.23.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of binary toluene acetylenic monomer, 43.7 mg (0.1 mmol) of binary trimethylsilylacetylene monomer, and monoaryl aryliodonium monomer into a 10 mL polymerization tube with side arms. 46.8mg (0.2mmol), 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen for three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 4 hours. After the reaction was completed and returned to room temperature, it was diluted with 10 mL of chloroform, and the solution was dropped into 200 mL of vigorously stirred methanol solution through a dropper plugged with cotton. Stand still, filter, and dry to constant weight to obtain a polymer with a yield of 55.5%. GPC results showed: _Mw = 27800, PDI = 4.03.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 3

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer

Add 6.76g (40mmol) fluorene to a 250mL two-necked bottle equipped with a condensing device, then add 100mL glacial acetic acid, 20mL water and 3mL concentrated sulfuric acid. The reaction solution was heated to 140° C. to dissolve all the reactants. After all the solution was dissolved, the reaction solution was cooled to 65° C., 8.17 g (32 mmol) of iodine and 3.89 g (16.7 mmol) of iodic acid were added, and the reaction was carried out for 4 hours. After the reaction solution was cooled to room temperature, it was extracted with ethyl acetate, and the collected organic phase was washed with saturated sodium carbonate and sodium thiosulfate pentahydrate. The obtained organic phase was dried with anhydrous magnesium sulfate; suction filtered and concentrated to obtain a crude product, which was recrystallized with ethyl acetate to obtain 12.47 g of light yellow 2,7-diiodo-fluorene with higher purity (74.8% yield) . Add 4.18g (10mmol) 2,7-diiodo-fluorene, 50mL DMSO to a 250mL double-necked round bottom flask equipped with a condensing device, heat to dissolve, then add 4.25g (22mmol) 1-bromooctane, 0.16g (0.5mmol) tetrabutylammonium bromide, stirred overnight at room temperature, after the reaction was completed, 1M hydrochloric acid solution was added dropwise to the reaction solution until the solution turned light yellow, extracted with anhydrous ether, and then dried with anhydrous magnesium sulfate. phase, suction filtration, and concentration to obtain a crude product, which was separated and purified by column chromatography, and dried in vacuum to constant weight to obtain 3.95 g of white solid 2,7-diiodo-9,9-dioctyl-fluorene (yield: 61.3% ).

Add 3.22g (5mmol) 2,7-diiodo-9,9-dioctyl-fluorene, 0.158g (0.6mmol) triphenylphosphine, 0.076g (0.4mmol) ) cuprous iodide, 0.140g (0.2mmol) bistriphenylphosphine palladium dichloride, vacuumize and fill with nitrogen three times. Add 20mL tetrahydrofuran and 80mL triethylamine and stir to dissolve, add 1.18g (12mmol) trimethylsilylacetylene in batches, stir and react overnight, filter with diatomaceous earth after the reaction, wash with triethylamine, and spin the filtrate to dryness , to obtain a crude product, which was separated and purified by column chromatography, and vacuum-dried to constant weight to obtain 1.91 g (yield: 65.5%) of a light yellow solid, which is a binary trimethylsilylacetylene monomer. ¹ H NMR (300MHz, CDCl ₃ )δ7.60, 7.57, 7.46, 7.45, 7.43, 7.41, 1.95, 1.93, 1.91, 1.89, 1.24, 1.21, 1.19, 1.17, 1.14, 1.11, 1.08, 1.01, 0.84, 0.82 ,0.79,0.51,0.48,0.28.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of binary toluene acetylenic monomer, 58.3 mg (0.1 mmol) of binary trimethylsilylethyne monomer, and monoaryl aryliodonium monomer into a 10 mL polymerization tube with a side arm. 46.8mg (0.2mmol), 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen for three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 4 hours. After the reaction was completed and returned to room temperature, it was diluted with 10 mL of chloroform, and the solution was dropped into 200 mL of vigorously stirred methanol solution through a dropper plugged with cotton. Stand still, filter, and dry to constant weight to obtain a polymer with a yield of 58.8%. GPC results showed: _Mw = 35900, PDI = 4.13. ¹ H NMR (300MHz, CDCl ₃ )δ7.42,7.36,7.17,7.00,6.80,6.77,6.75,6.62,6.32,3.88,3.82,3.74,3.66,1.73,1.43,1.35,1.30,1.18,0.82,0.80 ,0.78,0.75.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 4

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomers

Add 3.22g (5mmol) 2,7-diiodo-9,9-dioctyl-fluorene, 0.158g (0.6mmol) triphenylphosphine, 0.076g (0.4mmol) ) cuprous iodide, 0.140g (0.2mmol) bistriphenylphosphine palladium dichloride, vacuumize and fill with nitrogen three times. Add 20mL tetrahydrofuran and 80mL triethylamine and stir to dissolve, add 1.12g (11mmol) phenylacetylene in batches, stir and react overnight, filter, wash with triethylamine, and spin the filtrate to obtain a crude product. Separation and purification, and vacuum drying to constant weight yielded 2.07 g (yield: 69.8%) of a light yellow solid, which is a binary tolanin monomer. ¹ H NMR (300MHz, CDCl ₃ ) δ7.69, 7.66, 7.59, 7.57, 7.55, 7.51, 7.38, 7.36, 2.01, 1.99, 1.98, 1.96, 1.56, 1.25, 1.22, 1.20, 1.18, 1.16, 1.13, 1.10 ,1.06,0.84,0.82,0.79,0.64,0.61,0.58.

(2) Preparation of binary trimethylsilylacetylene monomer: same as Example 1.

(3) Preparation of polyarylene

Add 59.1 mg (0.1 mmol) of binary toluene acetylenic monomer, 60.1 mg (0.1 mmol) of binary trimethylsilylacetylene monomer, 46.8mg (0.2mmol), 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen for three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 8 hours. After the reaction was completed and returned to room temperature, it was diluted with 10 mL of chloroform, and the solution was dropped into 200 mL of vigorously stirred methanol solution through a dropper plugged with cotton. Stand still, filter, and dry to constant weight to obtain a polymer with a yield of 78.1%. GPC results showed: _Mw = 24100, PDI = 2.80. ¹ H NMR (300MHz, CDCl ₃ )δ7.73,7.60,7.56,7.53,7.42,7.36,7.18,6.90,5.22,5.11,5.02,4.85,3.97,3.90,3.86,3.81,3.77,3.74,3.66,3.58 , 1.89, 1.68, 1.31, 1.23, 1.07, 0.89.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 5

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomer: same as Example 4.

(2) Preparation of binary trimethylsilylacetylene monomer: same as Example 2.

(3) Preparation of polyarylene

Add 59.1 mg (0.1 mmol) of binary toluene acetylenic monomer, 60.1 mg (0.1 mmol) of binary trimethylsilylacetylene monomer, 46.8mg (0.2mmol), 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen for three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 4 hours. After the reaction was completed and returned to room temperature, it was diluted with 10 mL of chloroform, and the solution was dropped into 200 mL of vigorously stirred methanol solution through a dropper plugged with cotton. Stand still, filter, and dry to constant weight to obtain a polymer with a yield of 41.4%. GPC results showed: _Mw = 19200, PDI = 2.74. ¹ H NMR (300 MHz, CDCl ₃ ) 7.55, 7.34, 7.24, 7.09, 6.95, 6.87, 6.63, 3.91, 3.84, 3.81, 3.72, 1.76, 1.65, 1.26, 1.16, 1.00, 0.85, 0.84, 0.81.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 6

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomer: same as Example 4.

(2) Preparation of binary trimethylsilylacetylene monomer: same as Example 3.

(3) Preparation of polyarylene

Add 59.1mg (0.1mmol) of binary toluene acetylenic monomer, 58.3mg (0.1mmol) of binary trimethylsilylacetylene monomer, 46.8mg (0.2mmol), 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen for three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 2 hours. After the reaction was completed and returned to room temperature, it was diluted with 10 mL of chloroform, and the solution was dropped into 200 mL of vigorously stirred methanol solution through a dropper plugged with cotton. Stand still, filter, and dry to constant weight to obtain a polymer with a yield of 63.0%. GPC results showed: _Mw = 6800, PDI = 1.94. ¹ H NMR (300MHz, CDCl ₃ )δ7.63,7.49,7.42,7.36,7.17,7.14,7.11,7.04,6.91,6.84,6.70,6.64,6.59,6.56,3.91,3.88,3.81,3.76,3.65,3.54 ,3.46,1.92,1.82,1.73,1.70,1.18,1.14,1.06,0.96,0.75,0.50.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 7

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomers

Add 7.83g (30mmol) of 4-bromobenzophenone and 7.80g (120mmol) of zinc powder into a 500mL two-necked flask equipped with a condensing device, vacuumize and fill with nitrogen three times. Add 150mL tetrahydrofuran and stir to dissolve, then transfer the reaction apparatus to an ice-water bath. Then 12.37 g (60 mmol) of titanium tetrachloride was slowly dropped into the flask, and reacted for 30 minutes under an ice-water bath. The reaction was then stirred overnight at reflux at 75°C. After the reaction was finished, the reaction device was lifted from the oil bath, and after cooling to room temperature, the remaining titanium tetrachloride was quenched with saturated potassium carbonate solution, then an appropriate amount of hydrochloric acid was added, extracted three times with dichloromethane, the organic phase was taken, and the Dry over anhydrous magnesium sulfate, filter with suction, and distill under reduced pressure to obtain the crude product, which is separated and purified by column chromatography, and vacuum-dried to constant weight to obtain 6.52 g of 1,4-dibromo-tetraphenylethylene as a white solid (yield: 88.7%). Add 2.45g (5mmol) 1,4-dibromo-tetraphenylethylene, 0.158g (0.6mmol) triphenylphosphine, 0.076g (0.4mmol) cuprous iodide into a 250mL two-necked flask equipped with a condensing device , 0.140g (0.2mmol) bistriphenylphosphine palladium dichloride, evacuated and filled with nitrogen three times. Add 20mL tetrahydrofuran and 80mL triethylamine and stir to dissolve, add 1.12g (11mmol) phenylacetylene in batches, stir and react overnight, filter, wash with triethylamine, and spin the filtrate to obtain a crude product. Separation and purification, and vacuum drying to constant weight yielded 1.27 g (yield: 47.9%) of a light yellow solid, which is a binary toluene monomer. ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.43, 7.42, 7.40, 7.23, 7.20, 7.17, 7.15, 7.07, 7.05, 7.04, 7.02, 6.96, 6.93, 6.91.

(2) Preparation of binary trimethylsilylacetylene monomer

Add 2.45g (5mmol) 1,4-dibromo-tetraphenylethylene, 0.158g (0.6mmol) triphenylphosphine, 0.076g (0.4mmol) cuprous iodide into a 250mL two-necked flask equipped with a condensing device , 0.140g (0.2mmol) bistriphenylphosphine palladium dichloride, evacuated and filled with nitrogen three times. Add 20mL tetrahydrofuran and 80mL triethylamine and stir to dissolve, add 1.12g (11mmol) phenylacetylene in batches, stir and react overnight, filter, wash with triethylamine, and spin the filtrate to obtain a crude product. Separation and purification, and vacuum drying to constant weight yielded 1.63 g (yield: 62.2%) of a light yellow solid, which is a binary trimethylsilylacetylene monomer. ¹ H NMR (300 MHz, CDCl ₃ ) 7.33, 7.26, 7.22, 7.21, 7.20, 7.19, 7.12, 7.10, 7.08, 7.02, 7.01, 7.00, 6.98, 6.94, 6.93, 6.91, 0.24, 0.22, 0.21.

(3) Preparation of polyarylene

Add 53.2 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 52.4 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times with vacuum and nitrogen; then add 0.8mL of dry DMF and 4μL of dry methanol, react at 100°C for 4 hours, dilute with 10mL of chloroform after the reaction is completed and return to room temperature, and pass the solution through the stopper The cotton dropper was added dropwise into 200 mL of vigorously stirred methanol solution, allowed to stand, filtered, and dried to constant weight to obtain a polymer with a yield of 67.5%. GPC results showed: M _w =5900, PDI=1.51. 1H NMR (300MHz, CDCl ₃ ) δ7.52, 7.50, 7.34, 7.12, 7.00, 3.91, 3.84, 3.82, 3.78, 3.71.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 8

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomer: same as Example 4.

(2) Preparation of binary trimethylsilylacetylene monomer: same as Example 7.

(3) Preparation of polyarylene

Add 59.1 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 52.4 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times with vacuum and nitrogen; then add 0.8mL of dry DMF and 4μL of dry methanol, react at 100°C for 4 hours, dilute with 10mL of chloroform after the reaction is completed and return to room temperature, and pass the solution through the stopper The cotton dropper was added dropwise into 200 mL of vigorously stirred methanol solution, allowed to stand, filtered, and dried to constant weight to obtain a polymer with a yield of 74.7%. GPC results showed: _Mw = 9600, PDI = 1.91.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 9

This embodiment relates to the preparation of a polyarylene, the synthesis method is as follows:

Include the following steps:

(1) Preparation of binary toluene monomer: same as Example 7.

(2) Preparation of binary trimethylsilylacetylene monomer: same as Example 3.

(3) Preparation of polyarylene

Add 53.2 mg (0.1 mmol) of binary toluene acetylenic monomer, 58.3 mg (0.1 mmol) of binary trimethylsilylethyne monomer, and 53.2 mg (0.1 mmol) of monoaryl aryliodonium monomer into a 10 mL polymerization tube with a side arm. 46.8mg (0.2mmol), 3.36mg (0.015mmol) of palladium acetate, 4.05mg (0.02mmol) of tri-tert-butylphosphine and 41.4mg (0.3mmol) of anhydrous potassium carbonate, vacuumize and inflate nitrogen for three times; then add 0.8 mL of dry DMF and 4 μL of dry methanol were reacted at 100°C for 4 hours. After the reaction was completed and returned to room temperature, it was diluted with 10 mL of chloroform, and the solution was dropped into 200 mL of vigorously stirred methanol solution through a dropper plugged with cotton. Stand still, filter, and dry to constant weight to obtain a polymer with a yield of 82.4%. GPC results showed: _Mw = 17100, PDI = 2.86. ¹ H NMR (300MHz, CDCl ₃ ) δ7.55, 7.53, 7.50, 7.48, 7.34, 7.32, 7.26, 7.09, 7.01, 6.91, 6.71, 3.98, 3.88, 3.85, 3.82, 3.78, 3.76, 3.73, 3.71, 3.69 , 1.58, 1.27, 1.11, 0.84, 0.81.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 10

This embodiment relates to the preparation of a polyarylenyne, using the same monomer as in Example 1, specifically as follows:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer: same as in Example 1.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 60.1 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times with vacuum and nitrogen; then add 1mL of dry DMAc and 5μL of dry methanol, react at 100°C for 4 hours, dilute with 10mL of chloroform after the reaction is completed and return to room temperature, and pass the solution through a cotton plug dropwise into 200 mL of vigorously stirred methanol solution, let stand, filter, and dry to constant weight to obtain a polymer with a yield of 91.1%. GPC results showed: _Mw = 12900, PDI = 2.22.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 11

This embodiment relates to the preparation of a polyarylenyne, using the same monomer as in Example 1, specifically as follows:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer: same as in Example 1.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 60.1 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times with vacuum and nitrogen; then add 1mL of dry DMF and 5μL of dry methanol, react at 100°C for 4 hours, dilute with 10mL of chloroform after the reaction is completed and return to room temperature, and pass the solution through a cotton plug dropwise into 200 mL of vigorously stirred methanol solution, let stand, filter, and dry to constant weight to obtain a polymer with a yield of 88.7%. GPC results showed: _Mw = 14600, PDI = 2.31.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 12

This embodiment relates to the preparation of a polyarylenyne, using the same monomer as in Example 1, specifically as follows:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer: same as in Example 1.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 60.1 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times with vacuum and nitrogen; then add 0.6mL dry DMF and 3μL dry methanol, react at 100°C for 4 hours, dilute with 10mL chloroform after the reaction is completed and return to room temperature, and pass the solution through the stopper The cotton dropper was added dropwise into 200 mL of vigorously stirred methanol solution, allowed to stand, filtered, and dried to constant weight to obtain a polymer with a yield of 41.6%. GPC results show: M _w = 47700, PDI = 6.36

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 13

This embodiment relates to the preparation of a polyarylenyne, using the same monomer as in Example 1, specifically as follows:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer: same as in Example 1.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 60.1 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times with vacuum and nitrogen; then add 0.8mL of dry DMF and 4μL of dry methanol, react at 80°C for 4 hours, dilute with 10mL of chloroform after the reaction is completed and return to room temperature, and pass the solution through the stopper The cotton dropper was added dropwise into 200 mL of vigorously stirred methanol solution, allowed to stand, filtered, and dried to constant weight to obtain a polymer with a yield of 78.8%. GPC results showed: _Mw = 9100, PDI = 1.63.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Example 14

This embodiment relates to the preparation of a polyarylenyne, using the same monomer as in Example 1, specifically as follows:

(1) Preparation of binary toluene monomer: same as Example 1.

(2) Preparation of binary trimethylsilylacetylene monomer: same as in Example 1.

(3) Preparation of polyarylene

Add 47.0 mg (0.1 mmol) of the binary toluene monomer of the first monomer and 60.1 mg (0.1 mmol) of the binary trimethylsilylacetylene monomer of the second monomer into a 10 mL polymerization tube with a side arm ( 0.1mmol), the third monovalent aryl iodide monomer 46.8mg (0.2mmol), palladium acetate 3.36mg (0.015mmol), tri-tert-butylphosphine 4.05mg (0.02mmol) and anhydrous potassium carbonate 41.4mg (0.3mmol), repeat three times by vacuuming and filling with nitrogen; then add 0.8mL dry DMF and 4μL dry methanol, react at 120°C for 4 hours, dilute with 10mL chloroform after the reaction is completed and return to room temperature, and pass the solution through the stopper The cotton dropper was added dropwise into 200 mL of vigorously stirred methanol solution, allowed to stand, filtered, and dried to constant weight to obtain a polymer with a yield of 87.2%. GPC results showed: _Mw = 18300, PDI = 2.44.

The polyarylenyne prepared in this example is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, etc. at room temperature, and has Good processability and film-forming properties. In addition, it has good thermal stability verified by thermogravimetric experiments.

Performance and Application

The polyarylenyne prepared by the invention can endow the polyarylenyne with AIE characteristics after introducing a structural unit with AIE activity, and can be used for the detection of nitroaromatic explosives and Ru ³⁺ .

(1) AIE features

Now take the polyarylenyne prepared in Example 7 as an example. The aggregation-induced luminescence characteristics test results of the polymer are shown in Figure 4. The polymer emits weakly in pure tetrahydrofuran solution. The fluorescence intensity of the polymer increases gradually, and the fluorescence intensity reaches the maximum at the water content of 90%, showing excellent aggregation-induced luminescent properties.

(2) Application in the detection of nitroaromatic explosives

Taking picric acid (PA) as a model explosive, using the polyarylene prepared by the present invention (taking the polymer prepared in Example 7 as an example) to detect PA, the specific operation is as follows: first prepare 10 ^-5 mol/ The THF aqueous solution (volume fraction of water: 90%) of L polyarylene was used as the detection object, and different amounts of the detection object PA were sequentially added to quickly test the fluorescence spectrum.

The detection results are shown in Figure 5, when no PA is added, the detection object has stronger fluorescence; after adding PA, the fluorescence weakens, and along with the addition of PA content increases sequentially, the fluorescence intensity gradually weakens, this phenomenon shows that the present invention The prepared polyarylene can be used as a sensor for detecting nitroaromatic explosives.

(3) Application in Ru ³⁺ detection

Use the polyarylene prepared by the present invention (taking the polymer prepared in Example 7 as an example) to detect Ru ³⁺ , the specific operation is as follows: prepare 10 ^-5 mol/L polyarylene in tetrahydrofuran aqueous solution (water The volume fraction is 90%) as the detection substance, adding different amounts of the detection substance Ru ³⁺ in sequence, and quickly testing the fluorescence spectrum.

The test results are shown in Figure 6. When no Ru ³⁺ is added, the detected object has strong fluorescence; after adding Ru ³⁺ , the fluorescence is weakened, and the fluorescence intensity gradually decreases with the increase of the Ru ³⁺ content. , this phenomenon indicates that the polyarylene prepared by the present invention can be used as a chemical sensor for detecting Ru ³⁺ .

The above-mentioned embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or transformations made by those skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the present invention shall be determined by the claims.

Claims (10)

1. A polyarylene, characterized in that, said polyarylene has the general structural formula:

Wherein, x and y are respectively selected from any integer ranging from 2 to 200; R and R' are respectively selected from any group shown in formula 1 to formula 22, and R" is selected from any group shown in formula 23 to formula 27; The structures of the groups represented by the above formulas 1 to 27 are as follows:

Wherein, m is selected from any integer ranging from 1 to 18. 2. a preparation method of polyarylene yne as claimed in claim 1, is characterized in that, under inert atmosphere, with the binary tolan monomer shown in formula (I), the formula (II) The binary trimethylsilylacetylene monomer shown and the monoaryl aryl iodide monomer shown in formula (III) react under the presence of organic ligand, palladium catalyst, acid-binding agent and solvent to obtain the polyaryl Enyne; The structures of the compounds shown in the above formulas (I) to (III) are as follows:

3. The preparation method according to claim 2, wherein the binary toluene monomer is prepared by the Sonogashira reaction of phenylacetylene and a binary halogenated aromatic compound; the binary trimethyl The silicon acetylene monomer is prepared by Sonogashira reaction between trimethylsilyl acetylene and a binary halogenated aromatic compound; the binary halogenated aromatic compound is X-R-X, and X is bromine or iodine. 4. The preparation method according to claim 2, characterized in that, the organic ligand is one of triphenylphosphine, tri-tert-butylphosphine, two (2-diphenylphosphine phenyl) ether or multiple; the palladium catalyst is one or more of palladium acetate, palladium dichloride, two (triphenylphosphine) palladium dichloride; the acid-binding agent is potassium carbonate, sodium carbonate, cesium carbonate One or more; The solvent is a mixed solvent of a polar aprotic solvent and methanol. 5. preparation method according to claim 4, is characterized in that, described polar aprotic solvent is N, N-dimethylformamide and/or N, N dimethylacetamide; The volume ratio of non-protic solvent to methanol is 100-300:1. 6. The preparation method according to claim 2, characterized in that, the binary toluene acetylenic monomer, the binary trimethylsiliconyl acetylenic monomer, the monoaryl iodide monomer, the organic ligand, The molar ratio of the palladium catalyst to the acid-binding agent is 1:1:2:0.15-0.3:0.025-0.2:2-4. 7. The preparation method according to claim 2, characterized in that the molar volume ratio of the reaction monomer to the solvent is 0.05˜0.25 mol:1L. 8. The preparation method according to claim 2, characterized in that, the reaction temperature is 60-150°C, and the reaction time is 0.5-24h. 9. The preparation method according to claim 2, characterized in that, the preparation method also includes a post-treatment process, specifically: adding chloroform to the polymer solution obtained by the reaction to obtain a mixed solution, and adding the mixed solution dropwise to methanol In, polyarylenynes were precipitated. 10. The application of the polyarylenyne according to claim 1 in detecting polynitroaromatic compounds and/or Ru ³⁺ , characterized in that, the polyarylenyne has a structural unit of AIE properties .

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