A polyarylacrylonitrile and a preparation method and application thereof

Abstract

The application discloses a kind of polyaryl acrylonitrile and its preparation method and application.The application obtains polyaryl acrylonitrile by carrying out polymerization reaction to multiple chalcone compounds and multiple aryl acetonitrile compounds in organic solvent under the action of base catalyst.The method of the application has mild conditions, no by-product, and the polymerization monomer is simple and easy to obtain, with high polymer yield, high molecular weight and good atom economy;The polyaryl acrylonitrile of the application has excellent processability and high thermal stability, as well as cluster light emitting performance, and can realize the sensitive detection of Fe (III) ion, and can be used in optical and sensing fields.

Description

Technical Field

[0001] This invention belongs to the field of polymer chemistry and materials science, specifically relating to a polyarylacrylonitrile, its preparation method, and its application. Background Technology

[0002] CH bonds are ubiquitous in nature, and direct conversion of CH bonds exhibits very high atom economy. In recent years, organic molecules prepared using CH activation have seen significant advancements in the biological and pharmaceutical fields. Furthermore, CH-activated polymerization methodologies, especially those based on C(sp...)... 3 The polymerization method of C(sp)-H activation is rarely reported. In recent years, Academician Tang Benzhong and Professor Qin Anjun's team reported a series of palladium(O)-catalyzed CH activation polymerization reactions guided by alkyne monomers, preparing a series of functional polymers (ACSMacro Lett. 2019, 8, 1068; Macromolecules 2020, 53, 3358). However, the use of transition metals may have some negative effects on polymers, such as reduced polymer solubility, quenching of luminescence, and biotoxicity. Therefore, the development of metal-free C(sp)-H activation polymerization methods is needed. 3 H-activated polymerization is of great significance. This invention achieves efficient polymerization of cyano-activated C-H bonds with biomass chalcone monomers catalyzed by alkali. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies of existing technologies, expand the range of biologically derived monomers, enrich the types of olefin monomers, and realize the application value of polymerization reactions of olefins and hydrocarbon monomers, the present invention aims to provide a polyaryl acrylonitrile and its preparation method and application; the present invention will provide a highly atom-economical polymerization method for preparing cluster-luminescent polyaryl acrylonitrile based on chalcone and hydrocarbon monomers through hydrocarbon activation, the polymerization reaction being simple, efficient and easy to operate.

[0004] Another objective of this invention is to provide a polyarylacrylonitrile prepared by the above method, which has good processing performance and thermal stability, and has good application prospects.

[0005] Another object of the present invention is to provide the application of the above-mentioned polyarylacrylonitrile.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A method for preparing polyarylacrylonitrile includes the following steps:

[0008] Polymerization of polyarylacrylonitrile compounds and polyaryl acetonitrile compounds in an organic solvent under the action of an alkaline catalyst yields polyarylacrylonitrile.

[0009] The poly-chalcone compounds contain at least two vinyl groups; the poly-arylacetonitrile compounds contain at least two cyano groups.

[0010] Preferably, the polychalcone compounds are as shown in formula (III) or (IV):

[0011]

[0012] The polyaryl acetonitrile compounds are shown in formula (V);

[0013]

[0014] The general structural formula of the polyarylacrylonitrile is shown in formula (I) or formula (II);

[0015]

[0016] Where n is an integer from 2 to 200, R 1 R 2 R 3 R 4 Each is an independent aromatic organic group.

[0017] Further preferred, R 1 R 2 Each is independently selected from any one of the following chemical structural formulas 1 to 20; R 3 R 4 Each can be independently selected from any one of structural formulas 21 to 41;

[0018]

[0019] Where m, h, i, j, k, and l are each independent integers from 1 to 20; X is selected from NH, O, or S elements; Y is selected from halogens; * indicates a substitution position.

[0020] Preferably, the organic solvent is at least one selected from dichloromethane, tetrahydrofuran, chloroform, acetonitrile, toluene, benzene, chlorobenzene, m-xylene, mesitylene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0021] More preferably, the organic solvent is dichloromethane. The resulting polyarylacrylonitrile has a higher molecular weight and better solubility, facilitating further application.

[0022] Preferably, the polymerization reaction is carried out in an atmosphere of air, oxygen, carbon dioxide, nitrogen, or an inert gas.

[0023] Preferably, the amount of the base catalyst is 5 to 200% of the molar amount of the polychalcone compound;

[0024] Preferably, the alkaline catalyst is at least one selected from sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, 1,8-diazobispyrocyclo[5.4.0]undecyl-7-ene (DBU), triethylenediamine (DABCO), 4-dimethylaminopyridine (DMAP), triethylamine (TEA), potassium tert-butoxide, n-butyllithium, sodium hydride, and potassium hydride.

[0025] Preferably, the molar ratio of vinyl groups in the poly-chalcone compounds to cyano groups in the poly-aryl acetonitrile compounds is (0.25–4):1;

[0026] Preferably, the concentration of the polychalcone compound in the organic solvent is 0.05–5 mol / L;

[0027] Preferably, the polymerization reaction temperature is 0–180°C; more preferably, the temperature is room temperature (10–35°C).

[0028] Preferably, the polymerization reaction takes 5 minutes to 36 hours. More preferably, the reaction takes 24 hours.

[0029] Preferably, the polymerization reaction is carried out at a rotation speed of 20-800 rpm.

[0030] Preferably, after the polymerization reaction is completed, the crude product is dissolved in organic solvent 1, and then a precipitant is added for precipitation. The precipitate is collected and dried to constant weight.

[0031] More preferably, the precipitant is at least one selected from water, methanol, ethanol, n-hexane, petroleum ether, diethyl ether, and acetone; the organic solvent 1 is at least one selected from dichloromethane, chloroform, and tetrahydrofuran; the ratio of the organic solvent 1 to the polychalcone compound is (0-1000) mL: (0.1-5) mmol; and the drying is vacuum drying at a temperature of 25-80°C.

[0032] The polyaryl acrylonitrile prepared by the above method is shown in the figure.

[0033] The above-mentioned applications of polyarylacrylonitrile as an optical material and in metal ion detection.

[0034] Preferably, the metal ion to be detected is Fe. 3+ .

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] (1) The preparation method of the present invention directly utilizes the hydrocarbon activation of multi-component chalcone monomers and the polymerization reaction of multi-component aryl acetonitrile monomers, thus it is innovative and of great significance.

[0037] (2) The reaction raw materials of the present invention are readily available and can be purchased directly or prepared through a simple reaction; the polymerization conditions are mild, the process is simple, the polymerization efficiency is high, and a high molecular weight polymer can be obtained by reacting at room temperature for only 6 hours.

[0038] (3) The preparation method of the present invention is completely atom-economical, and no by-products are generated during the polymerization process. It is a green polymerization that meets the atom-economic requirements.

[0039] (4) The polyarylacrylonitrile of the present invention exhibits fluorescence in both solution and aggregated states, and has the characteristic that the fluorescence wavelength varies with the excitation wavelength, making it suitable for use in optical materials; and Fe 3+ Fluorescence quenching after action can be used to detect Fe. 3 + At the same excitation wavelength, different concentrations exhibit wavelength-dependent PL spectra with concentration-dependent characteristics. Attached Figure Description

[0040] Figure 1 The images show the 1H NMR spectra of polyarylacrylonitrile P1, the model small molecule compound, and their corresponding monomers prepared in Example 1 in CDCl3; where A is the spectrum of monomer 1a, B is the spectrum of monomer 2a, C is the spectrum of the model compound, and D is the spectrum of polyarylacrylonitrile P1 prepared in Example 1.

[0041] Figure 2 The images show the carbon NMR spectra of polyarylacrylonitrile P1, the model small molecule compound, and their corresponding monomers prepared in Example 1 in CDCl3; where A is the spectrum of monomer 1a, B is the spectrum of monomer 2a, C is the spectrum of the model compound, and D is the spectrum of polyarylacrylonitrile P1 prepared in Example 1.

[0042] Figure 3 Thermogravimetric curve of polyarylacrylonitrile P1 prepared in Example 1;

[0043] Figure 4 The different fluorescence and photoluminescence spectra of polyarylacrylonitrile P1 prepared in Example 1;

[0044] Figure 5 The photoluminescence spectra of polyarylacrylonitrile P1 prepared in Example 1 at different concentrations with the same excitation wavelength are shown.

[0045] Figure 6 The fluorescence response diagrams of arylacrylonitrile P1 prepared in Example 1 interacting with different metal ions are shown.

[0046] Figure 7 Arylacrylonitrile P1 prepared in Example 1 and Fe of different concentrations 3+ Fluorescence intensity curves of ion interactions. Detailed Implementation

[0047] The present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. However, the implementation of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.

[0048] In the following examples, the room temperature is 10–35°C.

[0049] Example 1

[0050] The synthesis method of monomer 1a in this embodiment is as follows: A magnetic flask, isophthalaldehyde (1.34 g, 10 mmol) (commercially available, purchased from Anage Chemicals in this example), NaOH (1 g, 25 mmol) (commercially available, purchased from Maclean's Reagent in this example), and 40 mL of methanol were added. Acetophenone (2.4 g, 20 mmol) (commercially available, purchased from Anage Chemicals in this example) was added dropwise. After the addition was complete, the reaction was carried out at room temperature for 12 hours (rotation speed of 500 rpm). After the reaction was completed, the mixture was filtered, and the solid was dried in a vacuum oven to constant weight, yielding a white solid with a yield of 81.4%. The structure of 1a is... 2a is 1,4-phenyleneacetonitrile, which is commercially available; in this example, it was purchased from Anaiji Chemical.

[0051] A method for preparing polyarylacrylonitrile (P1) includes the following steps:

[0052] (1) Add a magnetic spool, monomer 1a (203.0 mg, 0.6 mmol), monomer 2a (93.7 mg, 0.6 mmol), and 1,8-diazobisspirocyclic [5.4.0]undec-7-ene (DBU) (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm); after the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0053] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P1.

[0054] Analysis of arylacrylonitrile showed that the yield of the final product, polyarylacrylonitrile P1, was 93.2%, with a weight-average molecular weight of 42,000 and a molecular weight distribution of 1.88.

[0055] Model compounds The preparation method was as follows: A rotor, chalcone (208 mg, 1 mmol) (commercially available, purchased from Amex Chemicals in this example), p-tolueneacetonitrile (157 mg, 1.2 mmol) (commercially available, purchased from Amex Chemicals in this example), DBU (30 μL, 0.2 mmol), and 1 mL of DMSO were added to a 7 mL polymerization tube, and the mixture was reacted at room temperature for 24 hours (500 rpm). After the reaction was complete, the mixture was extracted three times with DCM and water, retaining the organic phase. The solution was purified by silica gel using a petroleum ether / dichloromethane mixture (v / v, 1 / 1) as the eluent. A clear liquid was obtained in 94.1% yield.

[0056] Polyarylacrylonitrile P1 and its corresponding monomers and model compounds 1 H NMR spectra such as Figure 1 As shown (* represents solvent peaks). Model compound ( Figure 1 C) and P1 ( Figure 1 The characteristic peaks of the –CH– and –CH2– hydrogen atoms at positions 5, 6, 7 and 8, 9, 10 in D) are located at multiple chemical shifts from 3.06 to 4.65 ppm; the reason for the formation of multiple peaks is the multiple reconstruction caused by the continuous connection of two chiral carbons at positions 5, 7 and 8, 10. Figure 1 The integral number of hydrogen atoms in D in the polymer is consistent with the number of repeating structural units in the polymer. Figure 1 C and Figure 1 The positions of the peaks in D in the model match, which confirms the structure of polyarylacrylonitrile.

[0057] Polyarylacrylonitrile P1 and its corresponding monomers and model compounds 13 C NMR spectra as follows Figure 2 As shown. 1a( Figure 2 A) Model compound ( Figure 2 C) and P1 ( Figure 2 The chemical shifts of the carbon on the carbonyl group of C=O in D) are 188.48, 197.06, and 197.29, respectively. 2a( Figure 2 B) Model compound ( Figure 2 C) and P1 ( Figure 2 The carbon peaks of the C≡N group on D) are located at 117.47, 119.56, and 119.15, respectively. This proves the retention of C=O and C≡N bonds. Simultaneously, it can be seen that 2a( Figure 2 The chemical shift of the methylene group (B) in the model compound is 23.29. Figure 2 C) and polymer P1 ( Figure 2 The displacements of D) in the figure are 45.34 and 45.14, respectively. This demonstrates the conversion from –CH2– to –CH–. This indicates that the polymerization reaction has proceeded successfully.

[0058] Figure 3 The thermogravimetric analysis (TGA) of polyarylacrylonitrile P1 shows that the thermal decomposition temperature (the temperature corresponding to a 5% weight loss) is 308℃, indicating that the prepared polyarylacrylonitrile has good thermal stability.

[0059] Figure 4 DMF solution of polyarylacrylonitrile P1 (10 -2 The fluorescence emission spectra of the polymer solution (mol / L) under different wavelengths of excitation were analyzed, revealing atypical luminescence characteristics. It can be observed that the PL peak of the emission spectrum changes with the excitation wavelength, specifically exhibiting an excitation-dependent phenomenon where the emission peak red-shifts with the excitation wavelength.

[0060] Figure 5 The photoluminescence spectra of DMF solutions of polyarylacrylonitrile (P1) at different concentrations with the same excitation wavelength (460 nm) are shown. A redshift of the PL peak occurs with increasing concentration, exhibiting a concentration dependence previously unobserved in cluster-luminescent polymers. This demonstrates the potential for achieving multicolor luminescence through modulation.

[0061] Figure 6 DMF solution of polyarylacrylonitrile P1 (10 -3 The luminescence of Fe in the mol / L state and the quenching of different metal ions (0.6 mmol / L) show that Fe 3+ Ions can quench the fluorescence of polymer P1 (excitation wavelength 360 nm).

[0062] Figure 7 A DMF solution of arylacrylonitrile P1 (10 -3 mol / L) and different concentrations of Fe 3+ Fluorescence intensity curve of ion interaction (excitation wavelength 365 nm), Fe 3+ The ion concentration exhibits a good linear relationship with fluorescence intensity. The quenching constant is 809 L / mol in the range of 0–300 μmol / L, 6759 L / mol in the range of 300–700 μmol / L, and 46640 L / mol in the range of 700–1000 μmol / L. The detection limit is 5.1 × 10⁻⁶. -7 mol / L; showed sensitive Fe 3+ Performance in qualitative and quantitative ion detection.

[0063] Furthermore, this polyaryl acrylonitrile compound P1 is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating that it has excellent solubility and processability.

[0064] The structural formula of the polyarylacrylonitrile P1 is:

[0065]

[0066] This invention also systematically explored the effects of the type and amount of alkaline catalyst, monomer concentration, and polymerization time on the polymerization reaction. Specific data are shown in Table 1 (wherein the monomer concentration refers to the concentration of monomer 1a, and the concentrations of monomer 1a and 2a are the same; parameters and processes not given are the same as those in the preparation method described above).

[0067] Table 1. Optimization data for the polymerization of polyarylacrylonitrile

[0068]

[0069]

[0070] 1) Meta-bis-chalcone 1a reacts with 1,4-phenylacetonitrile 2a in air at room temperature. 2) Estimation was performed using GPC in DMF based on PMMA standard samples.

[0071] Example 2

[0072] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2a is 1,4-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0073] A method for preparing polyarylacrylonitrile (P1) includes the following steps:

[0074] (1) Add a magnetic flask, monomer 1a (9.14 g, 27 mmol), monomer 2a (4.22 g, 27 mmol), and DBU (820 mg, 5.4 mmol) to a 100 mL flask, then seal it with a rubber stopper and inject 45.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 50 mL with dichloromethane.

[0075] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 1000 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P1.

[0076] Analysis revealed that the final product, polyarylacrylonitrile P1, had a yield of 99.9%, a weight-average molecular weight of 19,600, and a molecular weight distribution of 1.84. The lower molecular weight compared to Example 1 is attributed to the reduced evaporation of the volatile solvent dichloromethane (DCM) on a larger scale. Unlike the small-scale reaction (1 mL), solvent evaporation becomes more controllable on a large scale, demonstrating the potential for large-scale production of this polyarylacrylonitrile.

[0077] The polyarylacrylonitrile P1 has the following structural formula:

[0078]

[0079] Example 3

[0080] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2b is 1,3-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0081] A method for preparing polyarylacrylonitrile (P2) includes the following steps:

[0082] (1) Add a magnetic particle, monomer 1a (203.0 mg, 0.6 mmol), monomer 2b (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0083] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P2.

[0084] Analysis revealed that the final product, polyarylacrylonitrile P2, had a yield of 90.2%, a weight-average molecular weight of 37,000, and a molecular weight distribution of 1.74. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0085] The polyarylacrylonitrile P2 has the following structural formula:

[0086]

[0087] Example 4

[0088] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2c is 5-methyl-1,3-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Maclean's reagent.

[0089] A method for preparing polyarylacrylonitrile (P3) includes the following steps:

[0090] (1) Add a magnetic particle, monomer 1a (203.0 mg, 0.6 mmol), monomer 2c (102 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm); after the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0091] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P3.

[0092] Analysis revealed that the final product, polyarylacrylonitrile P3, had a yield of 83.1%, a weight-average molecular weight of 24,000, and a molecular weight distribution of 1.67. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0093] The polyarylacrylonitrile P3 has the following structural formula:

[0094]

[0095] Example 5

[0096] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2d is phthalic anionyl nitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0097] A method for preparing polyarylacrylonitrile (P4) includes the following steps:

[0098] (1) Add a magnetic particle, monomer 1a (203.0 mg, 0.6 mmol), monomer 2d (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0099] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P4.

[0100] Analysis revealed that the final product, polyarylacrylonitrile P4, had a yield of 90.3%, a weight-average molecular weight of 28,000, and a molecular weight distribution of 1.66. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0101] The polyarylacrylonitrile P4 has the following structural formula:

[0102]

[0103] Example 6

[0104] The synthesis method of monomer 1b in this embodiment is as follows: A magnetic flask, terephthalaldehyde (1.34 g, 10 mmol) (commercially available, purchased from Anaiji Chemical in this example), NaOH (1 g, 25 mmol) (commercially available, purchased from Maclean's Reagent in this example), and 40 mL of methanol were added. Acetophenone (2.4 g, 20 mmol) (commercially available, purchased from Anaiji Chemical in this example) was added dropwise. After the addition was complete, the reaction was carried out at room temperature for 12 hours (rotation speed of 500 rpm). After the reaction, the mixture was filtered, and the solid was dried in a vacuum oven to constant weight. The solid was then passed through a silica gel column using dichloromethane:petroleum ether = 1:1 as the eluent, yielding a pale yellow solid with a yield of 66.3%. The structure of 1b is... 2a is 1,4-phenyleneacetonitrile, which is commercially available; in this example, it was purchased from Anaiji Chemical.

[0105] A method for preparing polyarylacrylonitrile (P5) includes the following steps:

[0106] (1) Add a magnetic particle, monomer 1b (203.0 mg, 0.6 mmol), monomer 2a (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0107] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P5.

[0108] Analysis revealed that the final product, polyarylacrylonitrile P5, had a yield of 96.6%, a weight-average molecular weight of 37,100, and a molecular weight distribution of 1.67. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0109] The polyarylacrylonitrile P5 has the following structural formula:

[0110]

[0111] Example 7

[0112] In this embodiment, the synthesis method of monomer 1b is the same as in Example 6; 2b is 1,3-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0113] A method for preparing polyarylacrylonitrile (P6) includes the following steps:

[0114] (1) Add a magnetic particle, monomer 1b (203.0 mg, 0.6 mmol), monomer 2b (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm); after the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0115] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P6.

[0116] Analysis revealed that the final product, polyarylacrylonitrile P6, had a yield of 88.1%, a weight-average molecular weight of 25,700, and a molecular weight distribution of 1.67. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0117] The polyarylacrylonitrile P6 has the following structural formula:

[0118]

[0119] Example 8

[0120] In this embodiment, the synthesis method of monomer 1b is the same as in Example 6; 2c is 5-methyl-1,3-phenyleneacetonitrile, which can be purchased commercially, and in this example it was purchased from Maclean's reagent.

[0121] A method for preparing polyarylacrylonitrile (P7) includes the following steps:

[0122] (1) Add a magnetic particle, monomer 1b (203.0 mg, 0.6 mmol), monomer 2c (102 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm); after the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0123] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P7.

[0124] Analysis revealed that the final product, polyarylacrylonitrile P7, had a yield of 86.0%, a weight-average molecular weight of 18,700, and a molecular weight distribution of 1.56. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0125] The polyarylacrylonitrile P7 has the following structural formula:

[0126]

[0127] Example 9

[0128] In this embodiment, the synthesis method of monomer 1b is the same as in Example 6; 2d is phthalic anionyl nitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0129] A method for preparing polyarylacrylonitrile (P8) includes the following steps:

[0130] (1) Add a magnetic particle, monomer 1b (203.0 mg, 0.6 mmol), monomer 2d (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0131] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P8.

[0132] Analysis revealed that the final product, polyarylacrylonitrile P8, had a yield of 95.1%, a weight-average molecular weight of 28,200, and a molecular weight distribution of 1.52. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0133] The polyarylacrylonitrile P8 has the following structural formula:

[0134]

[0135] Example 10

[0136] The synthesis method of monomer 1c in this embodiment is as follows: A magnetic magnet, 4,4'-biphenyldicarboxaldehyde (2.10 g, 10 mmol) (commercially available, purchased from Anaiji Chemical in this example), NaOH (1 g, 25 mmol) (commercially available, purchased from Maclean's Reagent in this example), and 40 mL of methanol were added to a 100 mL double-necked flask. Acetophenone (2.4 g, 20 mmol) (commercially available, purchased from Anaiji Chemical in this example) was added dropwise. After the addition was complete, the reaction was carried out at room temperature for 12 hours (rotation speed of 500 rpm). After the reaction was completed, the mixture was filtered, and the solid was dried in a vacuum oven to constant weight. The solid was then passed through a silica gel column using dichloromethane:petroleum ether = 1:1 as the eluent to obtain a pale yellow solid with a yield of 76.8%. The structure of 1c is... 2a is 1,4-phenyleneacetonitrile, which is commercially available; in this example, it was purchased from Anaiji Chemical.

[0137] A method for preparing polyarylacrylonitrile (P9) includes the following steps:

[0138] (1) Add a magnetic particle, monomer 1c (248.4 mg, 0.6 mmol), monomer 2a (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm); after the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0139] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P9.

[0140] Analysis revealed that the final product, polyarylacrylonitrile P9, had a yield of 95.6%, a weight-average molecular weight of 47,800, and a molecular weight distribution of 1.64. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0141] The polyarylacrylonitrile P9 has the following structural formula:

[0142]

[0143] Example 11

[0144] In this embodiment, the synthesis method of monomer 1c is the same as in Example 10; 2b is 1,3-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0145] A method for preparing polyarylacrylonitrile (P10) includes the following steps:

[0146] (1) Add a magnetic particle, monomer 1c (248.4 mg, 0.6 mmol), monomer 2b (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0147] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P10.

[0148] Analysis revealed that the final product, polyarylacrylonitrile P10, had a yield of 95.5%, a weight-average molecular weight of 60,200, and a molecular weight distribution of 1.89. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0149] The polyarylacrylonitrile P10 has the following structural formula:

[0150]

[0151] Example 12

[0152] In this embodiment, the synthesis method of monomer 1c is the same as in Example 10; 2c is 5-methyl-1,3-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Maclean's reagent.

[0153] A method for preparing polyarylacrylonitrile (P11) includes the following steps:

[0154] (1) Add a magnetic particle, monomer 1c (248.4 mg, 0.6 mmol), monomer 2c (102 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0155] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P11.

[0156] Analysis revealed that the final product, polyarylacrylonitrile P11, had a yield of 95.6%, a weight-average molecular weight of 35,800, and a molecular weight distribution of 1.83. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0157] The polyarylacrylonitrile P11 has the following structural formula:

[0158]

[0159] Example 13

[0160] In this embodiment, the synthesis method of monomer 1c is the same as in Example 10; 2d is phthalic anionyl nitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0161] A method for preparing polyarylacrylonitrile (P12) includes the following steps:

[0162] (1) Add a magnetic particle, monomer 1b (248.4 mg, 0.6 mmol), monomer 2d (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0163] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P12.

[0164] Analysis revealed that the final product, polyarylacrylonitrile P12, had a yield of 95.8%, a weight-average molecular weight of 34,000, and a molecular weight distribution of 1.62. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0165] The polyarylacrylonitrile P12 has the following structural formula:

[0166]

[0167] Example 14

[0168] In this embodiment, the synthesis method of monomer 1d is as follows: A magnetic flask, isophthalaldehyde (1.34 g, 10 mmol) (commercially available, purchased from Anaiji Chemical in this example), NaOH (1 g, 25 mmol) (commercially available, purchased from Maclean's Reagent in this example), and 40 mL of methanol were added. Then, 20 mL of methanol-dissolved p-methoxyacetophenone (3.0 g, 20 mmol) (commercially available, purchased from Anaiji Chemical in this example) was added dropwise. After the addition was complete, the reaction was carried out at room temperature for 12 hours (rotation speed of 500 rpm). After the reaction, the mixture was filtered, and the solid was dried in a vacuum oven to constant weight. The solid was then passed through a silica gel column using dichloromethane:petroleum ether = 1:1 as the eluent to obtain a white solid with a yield of 68.2%. The structure of 1d is... 2a is 1,4-phenyleneacetonitrile, which is commercially available; in this example, it was purchased from Anaiji Chemical.

[0169] A method for preparing polyarylacrylonitrile (P13) includes the following steps:

[0170] (1) Add a magnetic particle, monomer 1d (239.1 mg, 0.6 mmol), monomer 2a (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0171] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P13.

[0172] Analysis revealed that the final product, polyarylacrylonitrile P13, had a yield of 89.7%, a weight-average molecular weight of 12,500, and a molecular weight distribution of 1.50. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0173] The polyarylacrylonitrile P13 has the following structural formula:

[0174]

[0175] Example 15

[0176] In this embodiment, the synthesis method of monomer 1d is the same as in Example 14; 2b is 1,3-phenyleneacetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0177] A method for preparing polyarylacrylonitrile (P2) includes the following steps:

[0178] (1) Add a magnetic particle, monomer 1d (239.1 mg, 0.6 mmol), monomer 2b (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0179] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P14.

[0180] Analysis revealed that the final product, polyarylacrylonitrile P14, had a yield of 92.6%, a weight-average molecular weight of 12,200, and a molecular weight distribution of 1.58. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0181] The polyarylacrylonitrile P14 has the following structural formula:

[0182]

[0183] Example 16

[0184] In this embodiment, the synthesis method of monomer 1d is the same as in Example 14; 2c is 5-methyl-1,3-phenyleneacetonitrile, which can be purchased commercially, and in this example it was purchased from Maclean's reagent.

[0185] A method for preparing polyarylacrylonitrile (P15) includes the following steps:

[0186] (1) Add a magnetic particle, monomer 1d (239.1 mg, 0.6 mmol), monomer 2c (102 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0187] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P15.

[0188] Analysis revealed that the final product, polyarylacrylonitrile P15, had a yield of 85.0%, a weight-average molecular weight of 9,100, and a molecular weight distribution of 1.33. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0189] The polyarylacrylonitrile P15 has the following structural formula:

[0190]

[0191] Example 17

[0192] In this embodiment, the synthesis method of monomer 1d is the same as in Example 14; 2d is phthalic anionyl nitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0193] A method for preparing polyarylacrylonitrile (P16) includes the following steps:

[0194] (1) Add a magnetic particle, monomer 1d (239.1 mg, 0.6 mmol), monomer 2d (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0195] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P16.

[0196] Analysis revealed that the final product, polyarylacrylonitrile P16, had a yield of 85.5%, a weight-average molecular weight of 16,600, and a molecular weight distribution of 1.40. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0197] The polyarylacrylonitrile P16 has the following structural formula:

[0198]

[0199] Example 18

[0200] In this embodiment, the synthesis method of monomer 1e is as follows: A magnetic flask, benzaldehyde (1.31 g, 12.4 mmol) (commercially available, purchased from Anaiji Chemical in this example), NaOH (1 g, 25 mmol) (commercially available, purchased from Maclean's Reagent in this example), and 40 mL of methanol were added. 1,4-Diacetylbenzene (1 g, 6.2 mmol) (commercially available, purchased from Anaiji Chemical in this example) was added dropwise. After the addition was complete, the reaction was carried out at room temperature for 12 hours (rotation speed of 500 rpm). After the reaction, the mixture was filtered, and the solid was dried in a vacuum oven to constant weight. The solid was then passed through a silica gel column using dichloromethane:petroleum ether = 1:1 as the eluent to obtain a pale yellow solid with a yield of 73.5%. The structure of 1e is... 2a is 1,4-phenyleneacetonitrile, which is commercially available; in this example, it was purchased from Anaiji Chemical.

[0201] A method for preparing polyarylacrylonitrile (P17) includes the following steps:

[0202] (1) Add a magnetic particle, monomer 1e (203.0 mg, 0.6 mmol), monomer 2a (93.7 mg, 0.6 mmol), and DBU (18.2 mg, 0.12 mmol) to a 25 mL polymerization tube, then seal it with a rubber stopper and inject 1.0 mL of dichloromethane using a syringe; stir the reaction at room temperature for 24 hours (400 rpm). After the reaction is complete, dilute the reaction solution to 5 mL with dichloromethane.

[0203] (2) Under stirring conditions (300 rpm), the polymer solution was added dropwise to 100 mL of methanol, then allowed to stand (standing time was 12 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylacrylonitrile P17.

[0204] Analysis revealed that the final product, polyarylacrylonitrile P17, had a yield of 46.7%, a weight-average molecular weight of 3500, and a molecular weight distribution of 1.05. This polyarylacrylonitrile is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0205] The polyarylacrylonitrile P17 has the following structural formula:

[0206]

[0207] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing polyarylacrylonitrile, characterized in that, Includes the following steps: Polymerization of polyaryl chalcone compounds and polyaryl acetonitrile compounds in an organic solvent under the action of an alkaline catalyst yields polyaryl acrylonitrile. The polychalcone compounds are shown in formula (III) or (IV): (III)(IV); The polyaryl acetonitrile compounds are shown in formula (V); （V）； The general structural formula of the polyarylacrylonitrile is shown in formula (I) or formula (II); （Ⅰ）（Ⅱ） Where n is an integer from 2 to 200, R 1 R 2 R 3 R 4 Each is an independent aromatic organic group; R 1 R 2 Each is independently selected from any one of the following chemical structural formulas 1 to 20; R 3 R 4 Each can be independently selected from any one of structural formulas 21 to 41; Where m, h, i, j, k, and l are each independent integers from 1 to 20; X is selected from NH, O, or S elements; Y is selected from halogens; * indicates a substitution position.

2. The preparation method according to claim 1, characterized in that, The organic solvent is at least one selected from dichloromethane, tetrahydrofuran, chloroform, acetonitrile, toluene, benzene, chlorobenzene, m-xylene, mesitylene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide. The polymerization reaction is carried out in an atmosphere of air, oxygen, carbon dioxide, nitrogen, or an inert gas.

3. The preparation method according to claim 2, characterized in that, The organic solvent is dichloromethane.

4. The preparation method according to claim 1, characterized in that, The amount of the alkaline catalyst used is 5-200% of the molar amount of the poly-chalcone compound; The alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, 1,8-diazobispyrocyclo[5.4.0]undecyl-7-ene, triethylenediamine, 4-dimethylaminopyridine, triethylamine, potassium tert-butoxide, n-butyllithium, sodium hydride, and potassium hydride.

5. The preparation method according to claim 1, characterized in that, The molar ratio of vinyl groups in the poly-chalcone compounds to cyano groups in the poly-aryl acetonitrile compounds is (0.25~4):1; The concentration of the polychalcone compounds in organic solvents is 0.05~5 mol / L; The polymerization reaction temperature is 0~180 ℃; the polymerization reaction time is 5 min~36 h.

6. The preparation method according to claim 1, characterized in that, After the polymerization reaction is completed, the crude product is dissolved in organic solvent 1, and then a precipitant is added to precipitate the product. The precipitate is collected and dried to constant weight. The precipitant is at least one of water, methanol, ethanol, n-hexane, petroleum ether, diethyl ether, and acetone; the organic solvent 1 is at least one of dichloromethane, chloroform, and tetrahydrofuran; the ratio of organic solvent 1 to polychalcone compound is (0~1000) mL: (0.1~5) mmol, and organic solvent 1 is not 0; the drying is vacuum drying at a temperature of 25~80℃.

7. Polyarylacrylonitrile prepared by the preparation method according to any one of claims 1-6.

8. The application of the polyarylacrylonitrile according to claim 7 as an optical material for non-disease diagnosis and treatment, and in the detection of metal ions.

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