A polyarylbutenylene and a preparation method and application thereof

Abstract

The application discloses a polyarylbutene and a preparation method and application thereof. The polyarylbutene is obtained by polymerizing a multi-propargyl compound and a methylene compound in an organic solvent under the protection of inert gas. The method has mild conditions, the polymerized monomers are simple and easy to obtain, the polymer has high yield, high molecular weight, high atomic economy, and excellent regioselectivity and stereoselectivity. The polyarylbutene has excellent processability and high thermal stability, high refractive index, metal ion fluorescence quenching, and cell imaging, and can be applied to the fields of optics, detection, biology, medicine and environment.

Description

Technical Field

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

[0002] C–H activation, as a novel organic synthesis method, has made significant progress in the preparation of functional organic molecules in the fields of biology, medicine, and total synthesis; however, current polymerization methodologies based on C–H activation, especially those based on C(sp...), remain to be seen. 3 )–H activation has been rarely reported. Therefore, the development of C(sp)-H activation is needed. 3 The C(sp)-H activated polymerization method for preparing functionalized polymers is of great significance. Currently, Academician Tang Benzhong and Professor Qin Anjun's team have reported a method based on C(sp)-H activation to prepare functionalized polymers. 3 The polymerization of H-activated propyne monomers with hydroxy or amino monomers has successfully prepared a series of functional polyallyl ethers and polyallyl tertiary amines (ACS Macro Lett. 2019, 8, 1068; Macromolecules 2020, 53, 3358). Compared to hydroxy and amino monomers, sp 3 Hybridized C-H bonds are relatively inert in reactivity, and based on C(sp...) 3 The polymerization of H-activated propyne and methylene monomers has not been reported in the field of polymer science. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies of existing technologies, enrich the types of alkyne monomers, and realize the application value of polymerization reactions of alkyne and hydrocarbon monomers, the purpose of this invention is to provide a polyarylbutene and its preparation method and application; this invention will provide a method for preparing regio- and stereoregular E-type polyarylbutene based on propyne and hydrocarbon monomers through hydrocarbon activation, which is simple, efficient and easy to operate.

[0004] Another object of the present invention is to provide polyarylbutene prepared by the above method, which has good processability, thermal stability, film-forming properties, high fluorescence quantum efficiency and refractive index.

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

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

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

[0008] Polymerization of polypropynyl compounds and methylene compounds in an organic solvent under inert gas protection yields polyarylbutene;

[0009] The structural formula of the polypropynyl compound is any one of the formulas shown in formula (II):

[0010]

[0011] The methylene compound is shown in formula (Ⅲ);

[0012]

[0013] The structure of the polyarylbutene is any one of those shown in formula (Ⅰ);

[0014]

[0015] In equations (I) to (III), n is an integer from 2 to 200, and R 1 R 1’ R 1” R is an aromatic organic group. 2 R 3 These are the same or different electron-withdrawing organic groups.

[0016] Preferably, in formulas (I) to (III), R 1 Selected from any one of the following chemical structural formulas 1 to 20; R 1’ Selected from any one of structural formulas 21 to 23; R 1” Selected from any one of structural formulas 24 to 25; R 2 R 3 Selected from any one of structural formulas 26 to 34;

[0017]

[0018] Where m, h, i, j, k, l are integers from 1 to 20; X is selected from NH, O, or S elements; * indicates the substitution position.

[0019] Preferably, the organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene, benzene, chlorobenzene, m-xylene, mesitylene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0020] More preferably, the organic solvent is toluene; the resulting polyarylbutene has a higher molecular weight and better solubility, making it easier to apply in the next step.

[0021] Preferably, the polymerization reaction is carried out under the action of a palladium catalyst and an acid catalyst.

[0022] More preferably, the palladium catalyst is at least one selected from the following: bis(triphenylphosphine)palladium(II) dichloride, palladium(II) acetate, tetra(triphenylphosphine)palladium(O), 1,1'-bis(diphenylphosphine)ferrocene palladium(II) dichloride, palladium(II) chloride, [1,1'-bis(diphenylphosphine)ferrocene]palladium(II) dichloride dichloromethane adduct, tris(dibenzylideneacetone) dipalladium(O) and tris(dibenzylideneacetone) dipalladium(O)-chloroform adduct;

[0023] More preferably, the acid catalyst is at least one selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

[0024] More preferably, the amount of palladium catalyst used is 5-100% of the molar amount of the polypropynyl compound; the amount of acid catalyst used is 5-200% of the molar amount of the polypropynyl compound.

[0025] Preferably, the molar ratio of the propynyl group to the methylene group in the polypropynyl compound is (0.5-3):1;

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

[0027] Preferably, the polymerization reaction is carried out at a temperature of 20–180°C; more preferably, the temperature is carried out at a temperature of 80–140°C.

[0028] Preferably, the polymerization reaction takes 5 minutes to 36 hours. More preferably, the reaction takes 3 to 24 hours.

[0029] 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.

[0030] 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 polypropynyl compound is (5-10) mL: (0.1-5) mol; and the drying is vacuum drying at a temperature of 25-80°C.

[0031] The polyarylbutene prepared by the above method exhibits good thermal stability and excellent processability, showing promising application prospects.

[0032] The above-mentioned applications of polyarylbutene in optical materials, metal ion detection, and preparation of bioimaging reagents.

[0033] Preferably, the metal ion is Fe.3+ .

[0034] Preferably, the bioimaging is performed on HeLa cells.

[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 propyne monomers and the polymerization reaction of methylene 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 in just 3 hours.

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

[0039] (4) The polyarylbutene of the present invention exhibits bright fluorescence in both the solution and aggregated states, and the polymer film has a high refractive index and Fe... 3+ Fluorescence quenching after action allows for the detection of Fe. 3+ It also shows good biocompatibility and can be used for cell imaging. Attached Figure Description

[0040] Figure 1 The images show the 1H NMR spectra of polyarylbutene 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 polyarylbutene P1 prepared in Example 1.

[0041] Figure 2 The images show the carbon NMR spectra of polyarylbutene 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 polyarylbutene P1 prepared in Example 1.

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

[0043] Figure 4 The fluorescence response diagram of polyarylbutene P8 prepared in Example 8 interacting with different metal ions;

[0044] Figure 5 Cell imaging of polyarylbutene P8 prepared in Example 8;

[0045] Figure 6 The refractive index curve of the polyarylbutene P9 film prepared in Example 9. Detailed Implementation

[0046] 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.

[0047] Example 1

[0048] In this embodiment, monomer 1a can be synthesized according to the methods described in published literature (ACS Macro Lett. 2019, 8, 1068; Macromolecules 2020, 53, 3358). The structure of 1a is as follows: 2a is malononitrile, which is commercially available; in this example, it was purchased from Energi Chemicals.

[0049] A method for preparing polyarylbutene (P1) includes the following steps:

[0050] (1) Add a magnetic magnet, monomer 1a (93.2 mg, 0.2 mmol), monomer 2a (13.2 mg, 0.2 mmol), and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Then add tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heated metal block and stir for 6 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0051] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (standing time was 4 h), filtered, and vacuum dried to constant weight (drying temperature was 50 °C) to obtain polyarylbutene P1.

[0052] Analysis showed that the yield of polyarylbutene P1 was 95%, with a weight-average molecular weight of 26,300 and a molecular weight distribution of 2.40. If the reaction solvent was changed to 1,4-dioxane, dimethyl sulfoxide (DMSO), or N,N-dimethylformamide (DMF), the polymerization results were somewhat worse. Specifically, in 1,4-dioxane, the yield was 66%, the weight-average molecular weight was 8,500, and the molecular weight distribution was 1.47; in DMSO, the yield was 18%, the weight-average molecular weight was 3,800, and the molecular weight distribution was 1.08; and in DMF, the yield was 38%, the weight-average molecular weight was 4,300, and the molecular weight distribution was 1.12.

[0053] Model compounds The preparation method is based on the published literature (J.Am.Chem.Soc.1998,120,10262).

[0054] The NMR spectra of the polyarylbutene, its corresponding monomers, and model compounds (* represents solvent peaks) are shown below. Figure 1 , Figure 2 (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 polyarylbutene); Figure 1 This is a hydrogen spectrum. Figure 2 This is a carbon spectrum. From... Figure 1 The data confirms that the polymer is polyarylbutene, corresponding to the model small molecule allyl ether at chemical shifts of 6.73 and 6.25 ppm. Figure 1 C) and polyarylbutene ( Figure 1 The characteristic peaks of the two E-type hydrogen atoms on the D) vinyl group, with a coupling constant J = 16; the chemical shift of 2.91 ppm corresponds to the characteristic peak of the hydrogen atoms of the newly formed CH2; in the spectrum of propyne 1a monomer, the methyl group attached to the alkynyl group and the methylene group of the 2a monomer can be seen, with chemical shifts of 2.09 and 3.59 ppm, respectively. In the small molecule model compound ( Figure 1 C) and polyarylbutene ( Figure 1 It disappears or almost disappears from the spectrum of D). From Figure 2 As can be seen, the chemical shifts of the two carbons on the triple bond of the propyne monomer and the methyl carbon attached to the alkyne are 85.91, 80.64, and 4.44 ppm, respectively, and the carbon shift of the methylene group of malononitrile is 8.78 ppm. In the small molecule model compound (… Figure 2 C) and polyarylbutene ( Figure 2 The carbon dioxide (C₂) disappeared from the carbon spectrum of the quaternary carbon (C₂), and the chemical shifts of the newly generated CH₂ and quaternary carbon were 40.49 and 40.48, respectively. This indicates that the polymerization reaction proceeded successfully and exhibited excellent regioselectivity and stereoselectivity.

[0055] Figure 3 The thermogravimetric analysis (TGA) of polyarylbutene P1 shows a thermal decomposition temperature (the temperature corresponding to a 5% weight loss) of 249℃, indicating that the prepared polyarylbutene has excellent thermal stability. P1 exhibits very good film-forming properties, with a refractive index of 1.6446 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P1 (water to DMF volume ratio 9:1) show good fluorescence emission (at a concentration of 10). -5The absolute fluorescence quantum yields were 15.8% and 4.6%, respectively. Furthermore, this polyarylbutene compound is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0056] The structural formula of the polyarylbutene P1 is:

[0057]

[0058] Example 2

[0059] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2b is methyl cyanoacetate, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0060] A method for preparing polyarylbutene (P2) includes the following steps:

[0061] (1) Add a magnetic magnet, monomer 1a (186.4 mg, 0.4 mmol) and benzoic acid (9.0 mg, 0.08 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (46.2 mg, 0.04 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject monomer 2b (39.6 mg, 0.4 mmol) and 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0062] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, and then allowed to stand (12 h). The supernatant was discarded, and the mixture was washed three times with n-hexane. The mixture was then vacuum dried to constant weight (50 °C) to obtain polyarylbutene P2.

[0063] Analysis revealed that the final product, polyarylbutene P2, had a yield of 53%, a weight-average molecular weight of 11,000, and a molecular weight distribution of 1.67. P2 exhibited excellent film-forming properties, with a refractive index of 1.6132 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P2 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 18.7% and 3.8%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0064] The polyarylbutene P2 has the following structural formula:

[0065]

[0066] Example 3

[0067] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2c is benzenesulfonyl acetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0068] A method for preparing polyarylbutene (P3) includes the following steps:

[0069] (1) Add a magnetic magnet, monomer 1a (186.4 mg, 0.4 mmol), monomer 2c (72.4 mg, 0.4 mmol), and benzoic acid (9.0 mg, 0.08 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (46.2 mg, 0.04 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0070] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P3.

[0071] Analysis revealed that the final product, polyarylbutene P3, had a yield of 88%, a weight-average molecular weight of 8100, and a molecular weight distribution of 1.58. P3 exhibited excellent film-forming properties, with a refractive index of 1.6436 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P3 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 9.6% and 4.2%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0072] The polyarylbutene P3 has the following structural formula:

[0073]

[0074] Example 4

[0075] In this embodiment, the synthesis method of monomer 1a is the same as in Example 1; 2d is bis(benzenesulfonate)methane, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0076] A method for preparing polyarylbutene (P4) includes the following steps:

[0077] (1) Add a magnetic magnet, monomer 1a (93.2 mg, 0.2 mmol), monomer 2d (59.2 mg, 0.2 mmol), and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0078] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P4.

[0079] Analysis showed that the final product, polyarylbutene P4, had a yield of 99%, a weight-average molecular weight of 73,200, and a molecular weight distribution of 4.36. P4 exhibited excellent film-forming properties, with a refractive index of 1.6457 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P4 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 7.4% and 12.8%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0080] The polyarylbutene P4 has the following structural formula:

[0081]

[0082] Example 5

[0083] In this embodiment, monomer 1b can be synthesized using the same method as 1a, yielding a pale yellow solid with a yield of 86%; 2a is malononitrile, which can be purchased commercially, and in this example, it was purchased from Anaiji Chemical.

[0084] The structure of monomer 1b is

[0085] A method for preparing polyarylbutene (P5) includes the following steps:

[0086] (1) Add a magnetic magnet, monomer 1b (81.6 mg, 0.2 mmol), monomer 2a (13.2 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 3 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0087] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P5.

[0088] Analysis showed that the final product, polyarylbutene P5, had a yield of 99%, a weight-average molecular weight of 9700, and a molecular weight distribution of 1.72. P5 exhibited excellent film-forming properties, with a refractive index of 1.6994 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P5 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 1.3% and 4.4%, respectively. Furthermore, this polyarylbutene was readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0089] The polyarylbutene P5 has the following structural formula:

[0090]

[0091] Example 6

[0092] In this embodiment, the synthesis method of monomer 1b is the same as in Example 5; 2b is methyl cyanoacetate, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0093] A method for preparing polyarylbutene (P6) includes the following steps:

[0094] (1) Add a magnetic magnet, monomer 1b (81.6 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject monomer 2b (19.8 mg, 0.2 mmol) and 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0095] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P6.

[0096] Analysis revealed that the final product, polyarylbutene P6, had a yield of 99%, a weight-average molecular weight of 12,300, and a molecular weight distribution of 1.62. P6 exhibited excellent film-forming properties, with a refractive index of 1.6696 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P6 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 0.9% and 19.7%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0097] The polyarylbutene P6 has the following structural formula:

[0098]

[0099] Example 7

[0100] In this embodiment, the synthesis method of monomer 1b is the same as in Example 5; 2c is benzenesulfonyl acetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0101] A method for preparing polyarylbutene (P7) includes the following steps:

[0102] (1) Add a magnetic magnet, monomer 1b (81.6 mg, 0.2 mmol), monomer 2c (36.2 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0103] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P7.

[0104] Analysis showed that the final product, polyarylbutene P7, had a yield of 99%, a weight-average molecular weight of 5500, and a molecular weight distribution of 1.27. P7 exhibited excellent film-forming properties, with a refractive index of 1.6854 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P7 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 0.9% and 7.5%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0105] The polyarylbutene P7 has the following structural formula:

[0106]

[0107] Example 8

[0108] In this embodiment, the synthesis method of monomer 1b is the same as in Example 5; 2d is methane dibenzenesulfonate, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0109] A method for preparing polyarylbutene (P8) includes the following steps:

[0110] (1) Add a magnetic magnet, monomer 1b (81.6 mg, 0.2 mmol), monomer 2d (59.2 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0111] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P8.

[0112] Analysis revealed that the final product, polyarylbutene P8, had a yield of 94%, a weight-average molecular weight of 8800, and a molecular weight distribution of 1.62. P8 exhibited excellent film-forming properties, with a refractive index of 1.6891 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P8 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields of P8 were 1.1% and 15.3%, respectively. The high aggregated-state luminescence efficiency of P8 allows it to be used for the detection of metal ions, specifically 14 metal ions (Fe2+, Fe2+, Fe3 ... 3+ Cd 2+ K + Ca 2+ NH4 + Cr 3+ Mn 2+ Ni 2+ Co 2+ Sm 3+ Cu 2+ Zn 2+ Ce 3+ Mg 2 + The study found that the aggregated solution of P8 (water to DMF volume ratio 9:1) reacted with the addition of Fe. 3+ Subsequently, its fluorescence immediately quenched, while the other 13 metal ions (at the same concentration) showed no fluorescence response, with P8 having a concentration of 10. -5 M, the concentration of metal ions is 6 × 10⁻⁶ -3 M. For example Figure 4The upper and lower layers are solutions of P8 reacting with metal ions under fluorescent and ultraviolet light, respectively. Furthermore, P8 exhibits excellent cell compatibility and can be used for HeLa cell imaging (P8 concentration 8 × 10⁻⁶). -6 M), such as Figure 5 This polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0113] The polyarylbutene P8 has the following structural formula:

[0114]

[0115] Example 9

[0116] In this embodiment, monomer 1c can be synthesized according to the same method as 1a, yielding a pale yellow solid with a yield of 77%; 2a is malononitrile, which can be purchased from the market, and in this example, it was purchased from Anaiji Chemical.

[0117] The structure of monomer 1c is

[0118] A method for preparing polyarylbutene (P9) includes the following steps:

[0119] (1) Add a magnetic magnet, monomer 1c (64.2 mg, 0.2 mmol), monomer 2a (13.2 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 3 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0120] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P9.

[0121] Analysis showed that the final product, polyarylbutene P9, had a yield of 98%, a weight-average molecular weight of 9900, and a molecular weight distribution of 1.81. P9 exhibited excellent film-forming properties, with a refractive index of 1.7126 at 589 nm. Figure 6 Furthermore, both the DMF solution and aggregated state of P9 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5The absolute fluorescence quantum yields were 7.0% and 2.2%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0122] The polyarylbutene P9 has the following structural formula:

[0123]

[0124] Example 10

[0125] In this embodiment, the synthesis method of monomer 1c is the same as in Example 9; 2b is methyl cyanoacetate, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0126] A method for preparing polyarylbutene (P10) includes the following steps:

[0127] (1) Add a magnetic magnet, monomer 1b (64.2 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject monomer 2b (19.8 mg, 0.2 mmol) and 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0128] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P10.

[0129] Analysis showed that the final product, polyarylbutene P10, had a yield of 99%, a weight-average molecular weight of 19300, and a molecular weight distribution of 2.15. P10 exhibited excellent film-forming properties, with a refractive index of 1.6964 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P10 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 12.5% ​​and 5.7%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0130] The polyarylbutene P10 has the following structural formula:

[0131]

[0132] Example 11

[0133] In this embodiment, the synthesis method of monomer 1c is the same as in Example 9; 2c is benzenesulfonyl acetonitrile, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0134] A method for preparing polyarylbutene (P11) includes the following steps:

[0135] (1) Add a magnetic magnet, monomer 1b (64.2 mg, 0.2 mmol), monomer 2c (36.2 mg, 0.2 mmol) and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0136] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P11.

[0137] Analysis revealed that the final product, polyarylbutene P11, had a yield of 88%, a weight-average molecular weight of 8700, and a molecular weight distribution of 1.62. P11 exhibited excellent film-forming properties, with a refractive index of 1.7001 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P11 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 5.9% and 3.1%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability.

[0138] The polyarylbutene P11 has the following structural formula:

[0139]

[0140] Example 12

[0141] In this embodiment, the synthesis method of monomer 1c is the same as in Example 5; 2d is bis(benzenesulfonate)methane, which can be purchased from the market, and in this example it was purchased from Anaiji Chemical.

[0142] A method for preparing polyarylbutene (P12) includes the following steps:

[0143] (1) Add a magnetic magnet, monomer 1b (64.2 mg, 0.2 mmol), monomer 2d (59.2 mg, 0.2 mmol), and benzoic acid (4.5 mg, 0.04 mmol) to a 25 mL polymerization tube. Weigh tetra(triphenylphosphine)palladium (23.1 mg, 0.02 mmol) in an argon-protected glove box. Remove the polymerization tube sealed with a rubber stopper from the glove box and inject 1.0 mL of toluene using a syringe. Place the polymerization tube in a 100 °C heating block and stir for 24 hours (400 rpm). After the reaction is complete, cool to room temperature and dilute the reaction solution to 5 mL with dichloromethane.

[0144] (2) Under stirring conditions (600 rpm), the polymer solution was added dropwise to n-hexane, then allowed to stand (2 h), filtered, washed 3 times with n-hexane, and vacuum dried to constant weight (50 °C) to obtain polyarylbutene P12.

[0145] Analysis revealed that the final product, polyarylbutene P12, had a yield of 94%, a weight-average molecular weight of 44,600, and a molecular weight distribution of 5.68. P12 exhibited excellent film-forming properties, with a refractive index of 1.7029 at 589 nm. Furthermore, both the DMF solution and the aggregated state of P12 (water to DMF volume ratio 9:1) showed good fluorescence emission (at a concentration of 10). -5 The absolute fluorescence quantum yields were 5.3% and 4.9%, respectively. Furthermore, this polyarylbutene is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and diDMSO at room temperature, indicating excellent solubility and processability.

[0146] The polyarylbutene P12 has the following structural formula:

[0147]

[0148] 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 polyarylbutene, characterized in that, Includes the following steps: Polymerization of polypropynyl compounds and methylene compounds in an organic solvent under inert gas protection yields polyarylbutene; The structural formula of the polypropynyl compound is any one of the formulas shown in formula (II): （Ⅱ）； The methylene compound is shown in formula (Ⅲ); （Ⅲ）； The structure of the polyarylbutene is any one of those shown in formula (Ⅰ); （Ⅰ）； In equations (I) to (III), n is an integer from 2 to 200, and R 1 R 1’ R 1’’ R is an aromatic organic group. 2 R 3 They may be the same or different electron-withdrawing organic groups; In equations (I) to (III), R 1 Selected from any one of the following chemical structural formulas 1-4; R 1’ Choose any one of the five structural formulas; R 1’’ Choose any one of the six structural formulas; R 2 R 3 Choose from any one of structural formulas 7 to 9; Wherein, m and l are integers from 1 to 20; * indicates the substitution position; the organic solvent is at least one of tetrahydrofuran, dichloromethane, chloroform, 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 the presence of a palladium catalyst and an acid catalyst.

2. The preparation method according to claim 1, characterized in that: The organic solvent is toluene; The palladium catalyst is at least one of the following: bis(triphenylphosphine)palladium(II) dichloride, palladium(II) acetate, tetra(triphenylphosphine)palladium(O), 1,1'-bis(diphenylphosphine)ferrocene palladium(II) dichloride, palladium(II) chloride, [1,1'-bis(diphenylphosphine)ferrocene]palladium(II) dichloride dichloromethane adduct, tris(dibenzylideneacetone) dipalladium(O) and tris(dibenzylideneacetone) dipalladium(O) chloroform adduct; The acid catalyst is at least one selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

3. The preparation method according to claim 1, characterized in that: The amount of palladium catalyst used is 5-100% of the molar amount of the polypropynyl compound; the amount of acid catalyst used is 5-200% of the molar amount of the polypropynyl compound.

4. The method for preparing polyarylbutene according to claim 1, characterized in that: The molar ratio of the propynyl group to the methylene group in the polypropynyl compound is (0.5~3):1; The polymerization reaction is carried out at a temperature of 20~180 ℃ and for a time of 5 min~36 h.

5. 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.

6. The preparation method according to claim 5, characterized in that: 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 the polypropynyl compound is (5~10) mL: (0.1~5) mol; the drying is vacuum drying at a temperature of 25~80℃.

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

8. The application of the polyarylbutene according to claim 7 in optical materials, metal ion detection, and preparation of bioimaging reagents.

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