Polyyne selenoether polymer, preparation method and application thereof

Abstract

The application belongs to the field of polymer chemistry and material science, and discloses a kind of polyacetylene selenide polymer and a preparation method and application thereof.The polyacetylene selenide polymer has one of the structures shown in the following general formula.The application realizes multi-component polymerization of elemental selenium, terminal alkyne and halogenated hydrocarbon in a solvent through the activation of alkali, and obtains polyacetylene selenide after precipitation and drying.The polymerization method has the advantages of mild and efficient reaction conditions, safe and simple operation, green and economic, environmental friendliness, high polymerization reaction yield, and easy separation of the product.The prepared polyacetylene selenide has novel and unique structure, good stability, high thermal stability, and high refractive index, and can be applied to the fields of optical materials and optoelectronic devices.

Description

Technical Field

[0001] This invention belongs to the fields of polymer chemistry and materials science, and specifically relates to a class of polyacetylenic selenide polymers, their preparation methods, and applications. Background Technology

[0002] Polyselenoethers, as an important class of selenium-containing polymers, have found wide applications in drug release, antibacterial, anticancer, self-assembly materials, self-healing materials, and stimuli-responsive materials due to their dynamic and redox properties. Currently, the main synthetic methods for polyselenoethers are the ring-opening polymerization of γ-selenobutyrolactone with epoxides (Macromolecules, 2020, 53, 203-211), the enzyme-catalyzed ring-opening polymerization of macrocyclic monomers of selenium-containing carbonates (ACS Macro Lett., 2018, 7, 336-340), the stepwise polymerization of electrophilic selenide reagents generated in situ from diselenoethers with olefins (Polym. Chem., 2019, 10, 574-581), and the stepwise polymerization of halogenated hydrocarbons with sodium selenide (J. Polym. Sci. Part B: Polym. Lett., 1967, 5, 843-845). The selenium-containing monomers used in these polymerization methods are complex in structure, limited in variety, toxic, expensive, and have poor stability. Furthermore, they often require one or more steps of conversion from elemental selenium, which greatly limits the diversity of polyselenoether materials and their application development. Elemental selenium has advantages such as being readily available, low in toxicity, stable, and easy to operate, making it an ideal selenium source for synthesizing selenium-containing polymers. Therefore, converting elemental selenium into polyselenoethers through economical, green, efficient, and simple methods is of great significance. The C≡C functional group possesses a wide range of chemical properties. By introducing the C≡C functional group into selenium-containing polymers to prepare polyacetylenic selenide, a novel structure never before reported, the synthesis of this type of polymer will greatly enrich the variety of selenium-containing heterochain polymers and facilitate the exploration of their chemical properties and research into their application fields. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a class of polyacetylenic selenide polymers.

[0004] Another objective of this invention is to provide a method for preparing the above-mentioned polyacetylenic selenide polymer, which prepares the polyacetylenic selenide polymer through multi-component polymerization of elemental selenium, terminal alkynes, and haloalkanes.

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

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

[0007] A class of polyacetylenic selenide polymers having one of the structures described in the following general formula:

[0008]

[0009] Where n, m, and i are all relatively independent integers between 2 and 500; Equations 2 and 3 represent hyperbranched polymers;

[0010] Among them, R 1 Choose from any of the following chemical structural formulas:

[0011]

[0012] Among them, R 2 Choose from any of the following chemical structural formulas:

[0013]

[0014] Among them, R 3 Choose from any of the following chemical structural formulas:

[0015]

[0016] Among them, R 4 Choose from any of the following chemical structural formulas:

[0017]

[0018] R 1 R 2 R 3 R 4 In this context, j, k, l, and o are all integers from 1 to 30, and Ar is an aryl group. Preferably, the above-mentioned polyacetylenic selenide polymer has one of the following structures:

[0019]

[0020]

[0021] A method for preparing the above-mentioned polyacetylenic selenide polymer includes the following steps:

[0022] (1) In a protective atmosphere or air atmosphere, elemental selenium, terminal alkyne, halogenated hydrocarbon and base are added to an organic solvent to carry out a polymerization reaction to obtain a reaction mother liquor.

[0023] (2) Dissolve the reaction mother liquor described in step (1) in an organic solvent, then add it to a precipitant for precipitation, collect the precipitate, and dry it to constant weight to obtain the polyacetylenic selenide.

[0024] When preparing the polyacetylenic selenide polymer shown in Formula 1, the structural formula of the terminal acetylenic material in step (1) is CH≡CR. 1 -C≡CH, the structural formula of the haloalkane is XR 2 -X, where X represents a halogen, and X is one of Cl, Br, or I elements, preferably -Br, R. 1 and R 2 R in Equation 1 1 and R 2 Same definition;

[0025] When preparing the polyacetylenic selenide polymer shown in Formula 2, the structural formula of the terminal acetylenic material in step (1) is R. 3 -(C≡CH)3, the structural formula of the halohydrocarbon is XR 2 -X, where X represents a halogen, and X is one of Cl, Br, or I elements, preferably -Br, R. 2 and R 3 With R in Equation 2 2 and R 3 Same definition;

[0026] When preparing the polyacetylenic selenide polymer shown in Formula 3, the structural formula of the terminal acetylenic material in step (1) is CH≡CR. 1 -C≡CH, the structural formula of the haloalkane is R 4 -(X)3, where X represents a halogen, and X is one of Cl, Br, or I elements, preferably -Br, R. 1 and R 4 With R in Equation 2 1 and R 4 Same definition;

[0027] Preferably, the base in step (1) is at least one of pyridine, triethylamine, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, sodium methoxide, cesium fluoride, cesium carbonate, and n-butyllithium.

[0028] Preferably, the organic solvent in step (1) is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, 1,4-dioxane, 1,2-dichloromethane, 1,2-dichloroethane, acetonitrile, tetrahydrofuran, and N-methylpyrrolidone.

[0029] Preferably, in step (1), the concentration of the terminal alkyne monomer is 0.1-2.0 mol / L;

[0030] Preferably, in step (1), the molar ratio of terminal alkyne, elemental selenium, haloalkanes and base is 1:1-6:0.2-3:1-6;

[0031] Preferably, the gas atmosphere described in step (1) is nitrogen, a rare gas, or air;

[0032] Preferably, the polymerization reaction in step (1) is carried out at a temperature of 0-120°C;

[0033] Preferably, the polymerization reaction in step (1) takes 0.1-10 hours;

[0034] Preferably, the stirring speed during the polymerization reaction in step (1) is 200-1000 rpm;

[0035] Preferably, the organic solvent in step (2) is one or a mixture of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0036] Preferably, the precipitant in step (2) is methanol;

[0037] Preferably, the drying temperature in step (2) is 20-50°C.

[0038] In this invention, the yield of polyacetylenic selenide polymer is greater than or equal to 68%, preferably greater than or equal to 89%, and more preferably 89-96%.

[0039] The above-mentioned polyacetylenic selenide polymers have applications in optical materials and optoelectronic devices.

[0040] This invention employs a strategy of alkali-activated elemental selenium and terminal alkynes, enabling the high-yield polyalkyne selenide to be prepared by multi-component polymerization with halogenated hydrocarbons under relatively mild conditions.

[0041] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0042] (1) The polymerization conditions of the present invention are mild, green and economical, the process is simple, the polymerization efficiency is high, the yield is high and the chemical selectivity is good.

[0043] (2) The preparation method of the present invention does not require a metal catalyst, and only alkali can be used to promote the multi-component polymerization of terminal alkyne, elemental selenium and halogenated hydrocarbons to prepare polyalkyne selenide.

[0044] (3) The preparation method of the present invention has good universality and can be applied to a variety of different types of monomers.

[0045] (4) The prepared acetylsene selenide has a novel and unique structure, good stability and high thermal stability.

[0046] (5) It has a high refractive index. Attached Figure Description

[0047] Figure 1The image shows a comparison of the proton NMR spectra of the polyacetylenic selenide prepared in Example 1 of this invention with its monomer and model compound in CDCl3.

[0048] Figure 2 Comparison of the carbon NMR spectra of the polyacetylenic selenide prepared in Example 1 of this invention with the monomer and the model compound in CDCl3.

[0049] Figure 3 The thermogravimetric curve of polyacetylenic selenide prepared in Example 1 of the present invention is shown.

[0050] Figure 4 The image shows the DSC curve of the polyacetylenic selenide prepared in Example 1 of this invention.

[0051] Figure 5 The refractive index diagram is shown for the polyacetylenic selenide prepared in Example 1 of this invention. Detailed Implementation

[0052] The present invention will be further described in detail below with reference to embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0053] Unless otherwise specified, all reagents used in the examples are commercially available.

[0054] Example 1

[0055] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0056]

[0057] The polyacetylenic selenide P1 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0058]

[0059] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anage Chemicals. 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951);

[0060] The synthesis steps of the polyacetylenic selenide are as follows:

[0061] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. 1,6-Dibromohexane 3a (0.08 g, 0.315 mmol) was dissolved in 1.5 mL of DMF and added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0062] Analysis showed that the yield of polyacetylenic selenide polymer P1 was 90%, with a weight-average molecular weight of 14,000 g / mol and a molecular weight distribution of 2.01. IR (KBr disk), ν (cm -1 ):3039,2926,2858,2152,1600,1566,1500,1465,1390,1288,1242,1169,1108,1060,1012,940,827,724,639,585,530. 1 H NMR(500MHz, CDCl3)δ7.35(d,J=8.2Hz,4H),6.80(d,J=8.4Hz,4H),3.98-3.91(m, 4H),2.88-2.78(m,4H),1.91-1.82(m,4H),1.81-1.76(m,4H),1.54-1.46(m,8H). 13 C NMR (100MHz, CDCl3) δ159.22,133.42,115.75,114.54,99.46,68.30,67.98,30.09,29.52,29.25,28.86,25.97.

[0063] A comparison of the proton NMR spectra of this polyacetylenic selenide with its corresponding monomers and model compounds (* represents solvent peaks) is shown below. Figure 1 Its carbon NMR spectrum is comparable to Figure 2 .in, Figure 1In the proton NMR spectrum, the NMR peak of the terminal alkyne monomer is at δ2.99. In the spectra of the model compound and the polymer, this peak disappears, indicating a transformation of the terminal alkyne. In the carbon NMR spectrum, the characteristic carbon peaks of the terminal alkyne monomer (C≡C) have chemical shifts of δ75.84 and δ83.87. After transformation into the polymer, the peak positions are δ68.30 and δ99.46, which perfectly match the characteristic carbon peaks of the model compound (δ68.38 / 99.37), confirming the polymer's structure. Figure 3 and Figure 4 The thermogravimetric curve and DSC of P1 are shown below. Figure 3 It can be seen that the temperature corresponding to a 5% weight loss is 305℃. Figure 4 It can be seen that its glass transition temperature (T) g The temperature was 6℃, indicating that polyacetylenic selenide P1 has good thermal stability. Figure 5 Among them, polyacetylenic selenide P1 has a refractive index of 1.73 at 633 nm, which is much higher than that of commonly used optical plastics, and has potential applications in the fields of optics and optoelectronics.

[0064] Example 2

[0065] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0066]

[0067] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0068]

[0069] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anage Chemicals. 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951);

[0070] The synthesis steps of the polyacetylenic selenide are as follows:

[0071] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and t-BuOK (0.10 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated and purged with nitrogen three times. 1,6-Dibromohexane 3a (0.08 g, 0.315 mmol) was dissolved in 1.5 mL of DMF solution and added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times with methanol (5 × 20 mL). After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0072] Analysis showed that the yield of polyacetylenic selenide P1 was 89%, the weight-average molecular weight was 17,500 g / mol, and the molecular weight distribution was 2.12.

[0073] Example 3

[0074] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0075]

[0076] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0077]

[0078] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals; 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951).

[0079] The synthesis steps of the polyacetylenic selenide are as follows:

[0080] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0081] Analysis showed that the yield of polyacetylenic selenide P1 was 90%, the weight-average molecular weight was 15,200 g / mol, and the molecular weight distribution was 2.03.

[0082] Example 4

[0083] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0084]

[0085] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0086]

[0087] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals; 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951).

[0088] The synthesis steps of the polyacetylenic selenide are as follows:

[0089] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and KOH (0.05 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0090] Analysis showed that the yield of polyacetylenic selenide P1 was 75%, the weight-average molecular weight was 10,200 g / mol, and the molecular weight distribution was 1.72.

[0091] Example 5

[0092] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0093]

[0094] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0095]

[0096] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals; 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951).

[0097] The synthesis steps of the polyacetylenic selenide are as follows:

[0098] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and CH3ONa (0.05 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated and purged with nitrogen three times. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0099] Analysis showed that the yield of polyacetylenic selenide P1 was 89%, the weight-average molecular weight was 17,200 g / mol, and the molecular weight distribution was 1.86.

[0100] Example 6

[0101] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0102]

[0103] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0104]

[0105] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals; 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951).

[0106] The synthesis steps of the polyacetylenic selenide are as follows:

[0107] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and t-BuONa (0.09 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated and purged with nitrogen three times. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0108] Analysis showed that the yield of polyacetylenic selenide P1 was 91%, the weight-average molecular weight was 19300 g / mol, and the molecular weight distribution was 1.95.

[0109] Example 7

[0110] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0111]

[0112] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0113]

[0114] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals; 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951).

[0115] The synthesis steps of the polyacetylenic selenide are as follows:

[0116] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and Cs₂CO₃ (0.29 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0117] Analysis showed that the yield of polyacetylenic selenide P1 was 70%, the weight-average molecular weight was 12,300 g / mol, and the molecular weight distribution was 1.75.

[0118] Example 8

[0119] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0120]

[0121] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0122]

[0123] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals; 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951).

[0124] The synthesis steps of the polyacetylenic selenide are as follows:

[0125] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and n-BuLi (0.6 mL, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in 1.5 mL of a mixed solution of THF and added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0126] Analysis showed that the yield of polyacetylenic selenide P1 was 95%, the weight-average molecular weight was 21800 g / mol, and the molecular weight distribution was 2.01.

[0127] Example 9

[0128] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0129]

[0130] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0131]

[0132] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anage Chemicals. 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951);

[0133] The synthesis steps of the polyacetylenic selenide are as follows:

[0134] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 40 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0135] Analysis showed that the yield of polyacetylenic selenide P1 was 92%, the weight-average molecular weight was 17,200 g / mol, and the molecular weight distribution was 2.15.

[0136] Example 10

[0137] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0138]

[0139] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0140]

[0141] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anage Chemicals. 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951);

[0142] The synthesis steps of the polyacetylenic selenide are as follows:

[0143] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 80 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0144] Analysis showed that the yield of polyacetylenic selenide P1 was 94%, the weight-average molecular weight was 20,200 g / mol, and the molecular weight distribution was 2.19.

[0145] Example 11

[0146] A polyacetylenic selenide polymer, the structural formula of which is shown in P1:

[0147]

[0148] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (I):

[0149]

[0150] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anage Chemicals. 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951);

[0151] The synthesis steps of the polyacetylenic selenide are as follows:

[0152] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. 1,6-Dibromohexane (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 120 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P1.

[0153] Analysis showed that the yield of polyacetylenic selenide P1 was 96%, the weight-average molecular weight was 20,000 g / mol, and the molecular weight distribution was 2.15.

[0154] Example 12

[0155] A polyacetylenic selenide polymer, the structural formula of which is shown on P2:

[0156]

[0157] The polyacetylenic selenide polymer is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (II):

[0158]

[0159] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3b is 1,11-dibromo-3,6,9-trioxaundecan, purchased from Bid Pharmaceuticals. 2a is a terminal alkyne, the synthesis method of which is described in the literature (Macromolecules 2015, 48, 1941-1951);

[0160] The synthesis steps of the polyacetylenic selenide are as follows:

[0161] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated and purged with nitrogen three times. 1,11-dibromo-3,6,9-trioxaundecanane 3b (0.10 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 40 °C. After the reaction was completed, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at a rotation speed of 1000 r / min. After standing, the precipitate was filtered and washed 5 times (5 × 20 mL) with methanol. After air drying, the solid powder was placed in a vacuum oven at 40 °C and dried for 24 h to obtain yellow powder P2.

[0162] Analysis showed that the yield of polyacetylenic selenide P2 was 91%, with a weight-average molecular weight of 29,300 g / mol and a molecular weight distribution of 1.92. IR (KBr disk), ν (cm -1 ):3040,2935,2863,2153,1602,1566,1504,1468,1391,1353,1286,1244,1172,1105,1015,830,645,588,533. 1 H NMR (400MHz, CDCl3) δ7.34(d,J=8.3Hz,4H),6.80(d,J=8.2Hz,4H),3.99-3.92(m,4H),3.90 -3.84(m,4H),3.69-3.64(m,8H),3.06-2.98(m,4H),1.84-1.76(m,4H),1.55-1.49(m,4H). 13 C NMR (150MHz, CDCl3) δ159.25,133.44,115.49,114.49,99.38,70.74,70.52,70.33,67.94,67.78,29.22,28.49,25.96.

[0163] Example 13

[0164] A polyacetylenic selenide polymer, the structural formula of which is shown on P3:

[0165]

[0166] The polyacetylenic selenide P3 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (III):

[0167]

[0168] 1 represents elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 2a represents terminal alkyne, synthesized as described in the literature (Macromolecules 2015, 48, 1941-1951); 3c represents a bromoalkane monomer, synthesized as described in the literature (Polym. Chem., 2021, 12, 1078-1085).

[0169] The synthesis steps of the polyacetylenic selenide polymer are as follows:

[0170] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2a (0.10 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated three times with nitrogen. Bromoalkane monomer 3c (0.14 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 40 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times with methanol (5 × 20 mL). After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P3.

[0171] Analysis showed that the yield of polyacetylenic selenide P3 was 89%, the weight-average molecular weight was 21,500 g / mol, and the molecular weight distribution was 1.88. IR (KBr disk), ν (cm -1 ):3041,2933,2858,2153,1602,1567,1506,1468,1390,1288,1241,1171, 1107,1023,828,775,729,640,585,530.1HNMR(500MHz,CDCl3)δ7.37-7.32 (m,4H),6.82-6.78(m,8H),3.94(t,J=6.4Hz,4H),3.89(t,J=6.3Hz,4H),2. 88-2.83(m,4H),1.93-1.84(m,4H),1.82-1.74(m,8H),1.56-1.48(m,12H). 13C NMR (100MHz, CDCl3) δ159.19,153.29,133.39,115.77,115.52,114.52,99. 41,68.55,68.35,67.97,30.18,29.58,29.39,29.24,29.23,25.97,25.70.

[0172] Example 14

[0173] A polyacetylenic selenide polymer, the structural formula of which is shown on P4:

[0174]

[0175] The polyacetylenic selenide P4 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (IV):

[0176]

[0177] 1 is elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 3a is 1,6-dibromohexane, purchased from Anaiji Chemical. 2b is terminal alkyne, and its synthesis method is as described in the literature (Macromolecules 2015, 48, 1941-1951).

[0178] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2b (0.11 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated three times with nitrogen. 1,6-Dibromohexane 3a (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 40 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P4.

[0179] Analysis showed that the yield of polyacetylenic selenide P4 was 93%, with a weight-average molecular weight of 27,600 g / mol and a molecular weight distribution of 2.28. IR (KBr disk), ν (cm -1):3055,3026,2925,2850,2150,1671,1597,1496,1442,1404,1238,1190,1106,1071,1022,973,915,834,758,699,615,572,526,475. 1 H NMR (500MHz, CDCl3) δ7.15-7.07(m,10H),7.02-6.97(m,4H),6.95-6.90(m,4H),2.87-2.77(m,4H),1.90-1.79(m,4H),1.50-1.42(m,4H). 13 C NMR (125MHz, CDCl3) δ143.61,143.19,140.99,131.47,131.39,131.09,130.96 ,128.05,127.89,126.97,126.87,121.71,99.78,70.89,30.03,29.54,28.77.

[0180] Example 15

[0181] A polyacetylenic selenide polymer, the structural formula of which is shown on page 5:

[0182]

[0183] The polyacetylenic selenide P5 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (V):

[0184]

[0185] 1 represents elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 2b represents terminal alkyne, synthesized as described in the literature (Macromolecules 2015, 48, 1941-1951); 3c represents a bromoalkane monomer, synthesized as described in the literature (Polym. Chem., 2021, 12, 1078-1085).

[0186] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2b (0.11 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. Bromoalkane monomer 3c (0.14 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 40 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain yellow powder P5.

[0187] Analysis showed that the yield of polyacetylenic selenide P5 was 95%, with a weight-average molecular weight of 32,200 g / mol and a molecular weight distribution of 1.83. IR (KBr disk), ν (cm -1 ):3050,3028,2928,2857,2150,1595,1502,1469,1392,1286,1225,1107,1028,977,911,827,760,734,700,616,572,523. 1 H NMR (400MHz, CDCl3) δ7.18-7.06(m,10H),7.02-6.97(m,4H),6.96-6.89(m,4H),6.82-6.77(m,4H),3 .89(t,J=6.1Hz,4H),2.85(t,J=6.9Hz,4H),1.95-1.80(m,4H),1.79-1.72(m,4H),1.53-1.44(m,8H). 13 CNMR (100MHz, CDCl3) δ153.23,143.58,143.18,140.95,131.47,131.38,131.07,130.94,128.03, 127.87,126.94,126.85,121.69,115.46,99.71,70.93,68.48,30.18,29.64,29.37,29.21,25.68.

[0188] Example 16

[0189] A polyacetylenic selenide polymer, the structural formula of which is shown on page 6:

[0190]

[0191] The polyacetylenic selenide P6 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (VI):

[0192]

[0193] 1 represents elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 2c represents a terminal alkyne, synthesized as described in the literature (Macromolecules 2015, 48, 1941-1951); 3c represents a bromoalkane monomer, synthesized as described in the literature (Polym. Chem., 2021, 12, 1078-1085).

[0194] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2c (0.09 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated three times with nitrogen. Bromoalkane monomer 3c (0.14 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at 40 °C. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain yellow powder P6.

[0195] Analysis showed that the yield of polyacetylenic selenide P6 was 92%, with a weight-average molecular weight of 39,700 g / mol and a molecular weight distribution of 2.10. IR (KBr disk), ν (cm -1 ):3035,2926,2856,2150,1588,1500,1392,1318,1279,1222,1176,1106,1032,907,825,754,724,694,645,609,529. 1 H NMR (400MHz, CDCl3) δ7.31-7.23(m,6H),7.10-7.03(m,3H),7.00-6.90(m,4H),6.83-6.75(m,4H) ,3.95-3.83(m,4H),2.92-2.77(m,4H),1.96-1.82(m,4H),1.81-1.71(m,4H),1.54-1.43(m,8H). 13C NMR (150MHz, CDCl3) δ153.21,147.18,146.72,132.91,129.66,125.52,124.24,1 23.30,117.59,115.43,99.41,69.63,68.47,30.18,29.66,29.38,29.23,25.70.

[0196] Example 17

[0197] A hyperbranched polyacetylenic selenide polymer, the structural formula of which is shown on page 7:

[0198]

[0199] The polyacetylenic selenide P7 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (VII):

[0200]

[0201] 1 is elemental selenium, which can be purchased commercially; in this example, it was purchased from Merrill Chemical Reagents. 2d is 1,3,5-triacetylenebenzene, purchased from Anaiji Chemicals; 3a is 1,6-dibromohexane, purchased from Anaiji Chemicals.

[0202] Selenium powder 1 (0.06 g, 0.75 mmol), triyne monomer 2d (0.02 g, 0.1 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the mixture was evacuated and purged with nitrogen three times. 1,6-Dibromohexane 3a (0.08 g, 0.315 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain a yellow powder, P7.

[0203] Analysis showed that the yield of polyacetylenic selenide P7 was 95%, the weight-average molecular weight was 42,200 g / mol, and the molecular weight distribution was 2.15.

[0204] Example 18

[0205] A hyperbranched polyacetylenic selenide polymer, the structural formula of which is shown on page 8:

[0206]

[0207] The polyacetylenic selenide P8 is prepared by direct reaction of elemental selenium, terminal alkyne, and haloalkanes, as shown in equation (viii):

[0208]

[0209] 1 represents elemental selenium, which is commercially available; in this example, it was purchased from Merrill Chemical Reagents. 2e represents 1,4-diethynylbenzene, purchased from Anaiji Chemicals; 3d represents 1,3,5-tris(bromomethyl)benzene, also purchased from Anaiji Chemicals.

[0210] Selenium powder 1 (0.06 g, 0.75 mmol), diyne monomer 2e (0.04 g, 0.3 mmol), and C2H5ONa (0.06 g, 0.9 mmol) were added sequentially to a 10 mL Shrek tube, and the tube was evacuated three times with nitrogen. 1,3,5-tris(bromomethyl)benzene 3d (0.04 g, 0.105 mmol) was dissolved in a mixture of 1.0 mL DMF and 0.5 mL THF, and then added to the reaction tube using a syringe. The mixture was stirred at 500 rpm for 3 h at room temperature. After the reaction was complete, 3 mL of DMF was added to the reaction solution for dilution. The diluted reaction solution was then filtered through cotton and added dropwise to 100 mL of methanol solution at 1000 rpm. After standing, the precipitate was filtered and washed five times (5 × 20 mL) with methanol. After air drying, the solid powder was dried in a vacuum oven at 40 °C for 24 h to obtain yellow powder P8.

[0211] Analysis showed that the yield of polyacetylenic selenide P8 was 91%, the weight-average molecular weight was 37,600 g / mol, and the molecular weight distribution was 2.11.

[0212] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A class of polyacetylenic selenide polymers, characterized in that... It has one of the structures shown in the following general formula: ， Where n, m, and i are all relatively independent integers between 2 and 500; Equations 2 and 3 represent hyperbranched polymers; Among them, R 1 Choose from any of the following chemical structural formulas: ， Among them, R 2 Choose from any of the following chemical structural formulas: ， Among them, R 3 Choose from any of the following chemical structural formulas: ， Among them, R 4 Choose from any of the following chemical structural formulas: ， R 1 R 2 R 3 R 4 In this context, j, k, l, and o are all integers from 1 to 30, and Ar represents aryl; The polyacetylenic selenide polymer is prepared by the following method: (1) In a protective atmosphere or air atmosphere, elemental selenium, terminal alkyne, halogenated hydrocarbon and base are added to an organic solvent to carry out a polymerization reaction to obtain a reaction mother liquor. (2) Dissolve the reaction mother liquor from step (1) in an organic solvent, then add a precipitant to precipitate, collect the precipitate, and dry it to constant weight to obtain the polyacetylenic selenide; In step (1), the concentration of the terminal alkyne monomer is 0.1-2.0 mol / L; In step (1), the molar ratio of terminal alkyne, elemental selenium, halogenated hydrocarbon and base is 1:1-6:0.2-3:1-6.

2. The polyacetylenic selenide polymer according to claim 1, characterized in that... It has one of the following structures: ， ， ， ， ， ， ， 。 3. The polyacetylenic selenide polymer according to claim 1, characterized in that: When preparing the polyacetylenic selenide polymer shown in Formula 1, the structural formula of the terminal acetylenic material in step (1) is CH≡CR. 1 -C≡CH, the structural formula of the haloalkane is XR 2 -X, where X represents a halogen, and X is one of the elements Cl, Br, or I, R 1 and R 2 R in Equation 1 1 and R 2 Same definition; When preparing the polyacetylenic selenide polymer shown in Formula 2, the structural formula of the terminal acetylenic material in step (1) is R. 3 -(C≡CH)3, the structural formula of the halohydrocarbon is XR 2 -X, where X represents a halogen, and X is one of the elements Cl, Br, or I, R 2 and R 3 With R in Equation 2 2 and R 3 Same definition; When preparing the polyacetylenic selenide polymer shown in Formula 3, the structural formula of the terminal acetylenic material in step (1) is CH≡CR. 1 -C≡CH, the structural formula of the haloalkane is R 4 -(X)3, where X represents a halogen, and X is one of the elements Cl, Br, or I. R 1 and R 4 With R in Equation 2 1 and R 4 The definitions are the same.

4. The polyacetylenic selenide polymer according to claim 3, characterized in that: When preparing the polyacetylenic selenide polymer shown in Formula 1, the structural formula of the terminal acetylenic material in step (1) is CH≡CR. 1 -C≡CH, the structural formula of the haloalkane is XR 2 -X, where X represents a halogen, X is -Br, and R... 1 and R 2 R in Equation 1 1 and R 2 Same definition; When preparing the polyacetylenic selenide polymer shown in Formula 2, the structural formula of the terminal acetylenic material in step (1) is R. 3 -(C≡CH)3, the structural formula of the halohydrocarbon is XR 2 -X, where X represents a halogen, X is -Br, and R... 2 and R 3 With R in Equation 2 2 and R 3 Same definition; When preparing the polyacetylenic selenide polymer shown in Formula 3, the structural formula of the terminal acetylenic material in step (1) is CH≡CR. 1 -C≡CH, the structural formula of the haloalkane is R 4 -(X)3, X is -Br, R 1 and R 4 With R in Equation 2 1 and R 4 The definitions are the same.

5. The polyacetylenic selenide polymer according to claim 1, characterized in that: The base mentioned in step (1) is at least one of pyridine, triethylamine, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, sodium methoxide, cesium fluoride, cesium carbonate, and n-butyllithium.

6. The polyacetylenic selenide polymer according to claim 1, characterized in that: The organic solvent in step (1) is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, 1,4-dioxane, 1,2-dichloromethane, 1,2-dichloroethane, acetonitrile, tetrahydrofuran, and N-methylpyrrolidone.

7. The polyacetylenic selenide polymer according to claim 1, characterized in that: The protective atmosphere or air atmosphere mentioned in step (1) is nitrogen, rare gas or air; The polymerization reaction in step (1) is carried out at a temperature of 0-120℃; The polymerization reaction in step (1) takes 0.1-10 hours.

8. The polyacetylenic selenide polymer according to claim 1, characterized in that: The organic solvent in step (2) is one or a mixture of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. The precipitant in step (2) is methanol.

9. The application of the polyacetylenic selenide polymer according to claim 1 or 2 in optical materials and optoelectronic devices.

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