Polyalkyne selenide compound as well as preparation method and application thereof
Polyacetylenide compounds were successfully prepared by polymerization of 1,2-benzisoselenazole-3(2H)-one compounds and aromatic diyne compounds, which solved the problem of lack of polyacetylenide synthesis methods in the prior art, realized efficient and stable polymer synthesis, and had excellent refractive properties.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SOUTH CHINA UNIV OF TECH
- Filing Date
- 2026-04-02
- Publication Date
- 2026-05-19
AI Technical Summary
Existing technologies have not reported a method for synthesizing polyacetylenic selenide via two-component polymerization, and there is a lack of simple and efficient methods for preparing novel selenium-containing polymers.
Polymerization of 1,2-benzisoselenazole-3(2H)-one compounds and aromatic diyne compounds was carried out in dichloromethane under the catalysis of silver nitrate and ammonia, and the resulting polyacetylenes selenide compounds were obtained after post-treatment.
A mild polymerization reaction condition is provided, the process is simple and the polymerization efficiency is high. The synthesized polyacetylenic selenide compounds have high molecular weight, good thermal stability and high refractive properties, and are suitable for refractive materials.
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Figure CN122060170A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of polymer chemistry and materials science, and in particular to a polyacetylenic selenide compound, its preparation method, and its application. Background Technology
[0002] Selenium-containing polymers are a class of high-molecular materials incorporating selenium atoms into their main chain or side chains. Based on the unique chemical properties of selenium, such as low bond energy, dynamic reversibility, and sensitivity to redox reactions and radiation, these polymers possess numerous functionalities, leading to their widespread application in organic optoelectronic materials, precious metal recycling, lithium-selenium batteries, high refractive index materials, pharmaceuticals, and self-healing materials. Polyselenoethers, due to their dynamic and redox properties, are widely used as self-healing materials, stimulus-responsive materials, antibacterial and anticancer materials, and drug-releasing materials.
[0003] The C≡C functional group possesses a rich array of chemical properties. Linking the C≡C functional group with selenium atoms promises to yield unique redox properties, chemical transformation reactions, and metal coordination properties. Polyacetylenate, prepared by introducing the chemically rich and widely applicable alkynyl group into the polyselenate structure, not only possesses a high refractive index due to the synergistic effect of aromatic rings, carbon-carbon triple bonds, and heteroatoms in its main chain, but more importantly, it offers exceptional modifiability and functional tunability derived from the alkynyl group and elemental selenium. This is expected to expand the library of selenium-containing polymer structures and lead to even more unique functional applications.
[0004] Currently, there are no reported methods for synthesizing polyacetylenic selenide via two-component polymerization. Developing a simple and efficient method for preparing novel selenium-containing polymer polyacetylenic selenide is of significant scientific importance and application value. Summary of the Invention
[0005] The purpose of this invention is to provide a polyacetylenic selenide compound, its preparation method, and its application, in order to solve the above-mentioned technical problems.
[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a polyacetylenic selenide compound having the following general structural formula: ; Where n is an integer between 2 and 400, and R is one of alkyl, substituted or unsubstituted aromatic groups.
[0007] Furthermore, the polyacetylenic selenide compound is selected from one of the following compounds: , , , , .
[0008] This invention also provides a method for preparing polyacetylenic selenide compounds, comprising the following steps: 1,2-benzisexazole-3(2H)-one compounds and aromatic diyne compounds were polymerized in dichloromethane under the catalysis of silver nitrate and ammonia. After the reaction was completed, the polyyne selenide compounds were obtained through post-treatment.
[0009] Furthermore, the aromatic diyne compound is selected from one of the following structural formulas: .
[0010] Furthermore, the 1,2-benzisoselenazole-3(2H)-ketone compound is selected from one of the following structural formulas: .
[0011] Furthermore, the molar ratio of the 1,2-benzisoselenazole-3(2H)-one compound and the aromatic diyne compound is 1:1 to 1.5.
[0012] Furthermore, the concentration of the aromatic diyne compound in dichloromethane is 0.05~1.00 mol / L; The molar ratio of silver nitrate to 1,2-benzisoselenazole-3(2H)-one compounds is 0.1~0.5:1; the molar ratio of ammonia to 1,2-benzisoselenazole-3(2H)-one compounds is 2~5:1.
[0013] Furthermore, the polymerization reaction is carried out under stirring conditions, with a stirring speed of 200~500 rpm; the polymerization temperature is 0~60℃, and the reaction time is 0.5~12h.
[0014] Furthermore, the post-processing steps are as follows: after the reaction is completed, the reaction solution is cooled, diluted with 1 to 4 times the volume of dichloromethane, and then the diluted solution is dropped into a settling agent for sedimentation. The precipitate is collected and dried at 40 to 60°C to constant weight. The settling agent is methanol or a mixed solution of methanol and saturated saline solution.
[0015] This invention also provides the application of polyacetylenic selenide compounds in refractive materials.
[0016] The beneficial effects of this invention are: (1) The preparation method of the present invention has mild polymerization reaction conditions, simple process and high polymerization efficiency.
[0017] (2) The preparation method of the present invention is the first polymerization reaction, which has not been reported before. The synthesized polymer has a novel structure and can be used for main chain reconstruction to prepare polymers with new structures.
[0018] (3) The preparation method of the present invention has strong group tolerance and can introduce a variety of functional groups into the monomer.
[0019] (4) The polyacetylenic selenide compounds of the present invention have high molecular weight, good thermal stability and high refractive properties, and are expected to be used as refractive materials. Attached Figure Description
[0020] Figure 1 The images show the 1H NMR spectra of the polyacetylenic selenide compound and its corresponding monomer prepared in Example 1 of this invention in deuterated dimethyl sulfoxide, where A is the 1H NMR spectrum of 1,4-diethynylbenzene in deuterated dimethyl sulfoxide; B is the 1H NMR spectrum of 1,4-[bis(1,2-benzisisoselenoazole-3(2H)-one)]butane in deuterated dimethyl sulfoxide; C is the 1H NMR spectrum of the model small molecule of the acetylenic selenide compound in deuterated dimethyl sulfoxide; and D is the 1H NMR spectrum of the polyacetylenic selenide in deuterated dimethyl sulfoxide.
[0021] Figure 2 The images show the carbon NMR spectra of the polyacetylenic selenide compound and its corresponding monomer prepared in Example 1 of this invention in deuterated dimethyl sulfoxide, where A is the carbon NMR spectrum of 1,4-diethynylbenzene in deuterated dimethyl sulfoxide; B is the carbon NMR spectrum of 1,4-[bis(1,2-benzisisoselenoazole-3(2H)-one)]butane in deuterated dimethyl sulfoxide; C is the carbon NMR spectrum of the model small molecule of the acetylenic selenide compound in deuterated dimethyl sulfoxide; and D is the carbon NMR spectrum of the polyacetylenic selenide in deuterated dimethyl sulfoxide.
[0022] Figure 3 The images show the NMR selenium spectra of the polyacetylenic selenide compound and its corresponding monomer prepared in Example 1 of this invention in deuterated dimethyl sulfoxide, where A is the NMR selenium spectrum of 1,4-[bis(1,2-benzisoselenazole-3(2H)-one)]butane in deuterated dimethyl sulfoxide; B is the NMR selenium spectrum of the model small molecule of the acetylenic selenide compound in deuterated dimethyl sulfoxide; and C is the NMR selenium spectrum of the polyacetylenic selenide in deuterated dimethyl sulfoxide.
[0023] Figure 4 The images show the infrared absorption spectra of polyacetylenic selenide and model small molecules of acetylenic selenide compounds prepared in Example 1 of this invention. In the images, A is the infrared absorption spectrum of 1,4-diethynylbenzene, B is the infrared absorption spectrum of 1,4-[bis(1,2-benzisisoselenoazole-3(2H)-one)]butane, C is the infrared absorption spectrum of model small molecules of acetylenic selenide compounds, and D is the infrared absorption spectrum of polyacetylenic selenide prepared in Example 1.
[0024] Figure 5The thermogravimetric curve of the polyacetylenic selenide prepared in Example 1 of the present invention is shown.
[0025] Figure 6 The refractive index diagrams are for the polyacetylenic selenide compounds P1 and P3-P4 prepared in Examples 1 and 3-4. Detailed Implementation
[0026] This invention provides a polyacetylenic selenide compound having the following general structural formula: ; Where n is an integer between 2 and 400, and R is one of alkyl, substituted or unsubstituted aromatic groups.
[0027] In this invention, n is preferably an integer between 50 and 300, and R is preferably alkyl, phenyl, biphenyl, or pyridyl.
[0028] In this invention, the polyacetylenic selenide compound is selected from one of the following compounds: , , , , .
[0029] This invention also provides a method for preparing polyacetylenic selenide compounds, comprising the following steps: 1,2-benzisexazole-3(2H)-one compounds and aromatic diyne compounds were polymerized in dichloromethane under the catalysis of silver nitrate and ammonia. After the reaction was completed, the polyyne selenide compounds were obtained through post-treatment.
[0030] In this invention, the preparation equation for the polyacetylenic selenide compounds is as follows: .
[0031] In this invention, the aromatic diyne compound is preferably selected from one of the following structural formulas: .
[0032] In this invention, the 1,2-benzisoselenazole-3(2H)-ketone compound is preferably selected from one of the following structural formulas: .
[0033] In this invention, the molar ratio of the 1,2-benzisoselenazole-3(2H)-one compound and the aromatic diyne compound is 1:1 to 1.5, preferably 1:1.1 to 1.4, and more preferably 1:1.2 to 1.3.
[0034] In this invention, the concentration of the aromatic diyne compound in dichloromethane is 0.05~1.00 mol / L, preferably 0.7~0.8 mol / L, and more preferably 0.3~0.5 mol / L; The molar ratio of silver nitrate to 1,2-benzisoselenazole-3(2H)-one compounds is 0.1~0.5:1, preferably 0.1~0.3:1; the molar ratio of ammonia to 1,2-benzisoselenazole-3(2H)-one compounds is 2~5:1, preferably 3:1.
[0035] In this invention, the polymerization reaction is carried out under stirring conditions, with a stirring speed of 200-500 rpm, preferably 300-400 rpm, and more preferably 350 rpm; the polymerization reaction temperature is 0-60℃, preferably 5-55℃, and more preferably 10-40℃; and the reaction time is 0.5-12h, preferably 1-10h, and more preferably 2-8h.
[0036] In this invention, the post-processing steps are as follows: after the reaction is completed, the reaction solution is cooled and diluted with 1 to 4 times the volume of dichloromethane, preferably 2 to 3 times; then the diluted solution is dropped into a settling agent for sedimentation, the precipitate is collected and dried at 40 to 60°C to constant weight, preferably at 50 to 55°C; the settling agent is methanol or a mixed solution of methanol and saturated saline solution, preferably methanol.
[0037] This invention also provides the application of polyacetylenic selenide compounds in refractive materials.
[0038] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0039] Example 1
[0040] A polyacetylenic selenide compound, the structural formula of which is shown in P1:
[0041] The polyacetylenic selenide is prepared by direct reaction of acetylenic, ketone and amine, as shown in formula (I):
[0042] Formula (1)
[0043] The monomer M1 is 1,4-[bis(1,2-benzisoselenazole-3(2H)-one)]butane. M2 is 1,4-diethynylbenzene, purchased from Energie.
[0044] The preparation steps of the polyacetylenic selenide are as follows: Add 45 mg (0.1 mmol) monomer M1, 13 mg (0.1 mmol) monomer M2, 10 mg (0.01 mmol) silver nitrate and 10 mg (0.3 mmol) ammonia to a polymerization tube, inject 2 mL of dichloromethane into the tube, and stir at 360 rpm for 8 hours at 25 °C. After the reaction is complete, dissolve the mother liquor in 2 mL of dichloromethane, then add it dropwise to methanol, let it stand, filter, and dry at 55 °C to constant weight to obtain polyacetylenic selenide P1.
[0045] Analysis showed that the yield of polyacetylenic selenide P1 was 96%, the weight-average molecular weight was 36,700, and the molecular weight distribution was 1.75.
[0046] The 1H NMR spectra of polyacetylenoid compound P1, its corresponding monomer, and model small molecules of acetylenoid ethers are as follows: Figure 1 Carbon NMR spectrum, such as Figure 2 Nuclear magnetic selenium spectrum such as Figure 3 Infrared absorption spectrum such as Figure 4 .
[0047] Proton NMR spectrum (400 MHz, DMSO-d6) δ (TMS, ppm): 8.90 (s, 2H), 8.13 (d,2H), 8.00 (d, 2H), 7.66-7.54 (m, 6H), 7.45-7.41 (m, 2H), 3.34 (s, 4H), 1.61(s, 4H).
[0048] Carbon NMR spectrum (100 MHz, DMSO-d6) δ (TMS, ppm): 166.84 (C=O), 132.85,132.51, 131.62, 130.23, 129.19, 128.14, 126.54, 122.70, 103.45, 78.51, 26.53.
[0049] Nuclear magnetic resonance selenium spectrum (114 MHz, DMSO-d6), δ 328.95.
[0050] The thermogravimetric curve of polyacetylenic selenide compound P1 is as follows: Figure 4 The thermal decomposition temperature with a 5% weight loss is 342℃.
[0051] Example 2
[0052] A polyacetylenic selenide compound, the structural formula of which is shown on P2:
[0053] The polyacetylenic selenide is prepared by direct reaction of acetylenic, ketone and amine, as shown in formula (II):
[0054] Formula (II)
[0055] Among them, monomer M1 is 1,4-[bis(1,2-benzisoselenazole-3(2H)-one)]butane. M3 is 4,4'-diethynylbiphenyl, purchased from Energie.
[0056] The preparation steps of the polyacetylenic selenide compound are as follows: Add 45 mg (0.1 mmol) monomer M1, 20 mg (0.1 mmol) monomer M3, 10 mg (0.01 mmol) silver nitrate and 10 mg (0.3 mmol) ammonia to a polymerization tube, inject 2 mL of dichloromethane into the tube, and stir at 360 rpm for 8 hours at 20 °C. After the reaction is complete, dissolve the mother liquor in 2 mL of dichloromethane, then add it dropwise to methanol, let it stand, filter, and dry at 55 °C to constant weight to obtain polyacetylenic selenide P2.
[0057] Analysis revealed that the yield of polyacetylenic selenide compound P2 was 88%, with a weight-average molecular weight of 74,300 and a molecular weight distribution of 2.14.
[0058] Example 3
[0059] A polyacetylenic selenide compound, the structural formula of which is shown on page 3:
[0060] The polyacetylenic selenide is prepared by direct reaction of acetylenic, ketone and amine, as shown in formula (III):
[0061] Formula (3)
[0062] Among them, monomer M1 is 1,4-[bis(1,2-benzisoselenazole-3(2H)-one)]butane. M4 is 1,3-diacetylenebenzene, purchased from Energie.
[0063] The preparation steps of the polyacetylenic selenide are as follows: Add 45 mg (0.1 mmol) monomer M1, 13 mg (0.1 mmol) monomer M4, 10 mg (0.01 mmol) silver nitrate and 10 mg (0.3 mmol) ammonia to a polymerization tube, inject 2 mL of dichloromethane into the tube, and stir at 360 rpm for 8 hours at 30 °C. After the reaction is complete, dissolve the mother liquor in 2 mL of dichloromethane, then add it dropwise to methanol, let it stand, filter, and dry at 55 °C to constant weight to obtain polyacetylenic selenide P3.
[0064] Analysis showed that the yield of polyacetylenic selenide P3 was 95%, the weight-average molecular weight was 24,700, and the molecular weight distribution was 1.88.
[0065] Example 4
[0066] A polyacetylenic selenide compound, the structural formula of which is shown on page 4:
[0067] The polyacetylenic selenide is prepared by direct reaction of acetylenic, ketone and amine, as shown in formula (iv):
[0068] Formula (IV)
[0069] Among them, monomer M1 is 1,4-[bis(1,2-benzisoselenazole-3(2H)-one)]butane. M5 is 2,6-bis(ethynyl)pyridine, purchased from Energie.
[0070] The preparation steps of the polyacetylenic selenide are as follows: Add 45 mg (0.1 mmol) monomer M1, 13 mg (0.1 mmol) monomer M5, 10 mg (0.01 mmol) silver nitrate and 10 mg (0.3 mmol) ammonia to a polymerization tube, inject 2 mL of dichloromethane into the tube, and stir at 360 rpm for 8 hours at 25 °C. After the reaction is complete, dissolve the mother liquor in 2 mL of dichloromethane, then add it dropwise to methanol, let it stand, filter, and dry at 55 °C to constant weight to obtain polyacetylenic selenide P4.
[0071] Analysis showed that the yield of polyacetylenic selenide P4 was 98%, the weight-average molecular weight was 19,500, and the molecular weight distribution was 1.56.
[0072] Example 5
[0073] A polyacetylenic selenide compound, the structural formula of which is shown on page 5:
[0074] The polyacetylenic selenide is prepared by direct reaction of acetylenic, ketone and amine, as shown in formula (V):
[0075] Formula (5)
[0076] Among them, monomer M1 is 1,4-[bis(1,2-benzisoselenazole-3(2H)-one)]butane. M6 is 1,7-octadiyne, purchased from Energie.
[0077] The preparation steps of the polyacetylenic selenide are as follows: Add 45 mg (0.1 mmol) of monomer M1, 11 mg (0.1 mmol) of monomer M6, 10 mg (0.01 mmol) of silver nitrate and 10 mg (0.3 mmol) of ammonia to a polymerization tube, inject 2 mL of dichloromethane into the tube, and stir at 360 rpm for 8 hours at 25 °C. After the reaction is complete, dissolve the mother liquor in 2 mL of dichloromethane, then add it dropwise to methanol, let stand, filter, and dry at 55 °C to constant weight to obtain polyacetylenic selenide P5.
[0078] Analysis showed that the yield of polyacetylenic selenide P5 was 83%, the weight-average molecular weight was 16,500, and the molecular weight distribution was 1.41.
[0079] As can be seen from the above embodiments, the present invention provides a method for preparing polyacetylenic selenide compounds. The raw materials for this preparation method are readily available, the polymerization conditions are mild, the process is simple, the polymerization efficiency is high, and the functional groups are highly tolerant, allowing for the introduction of various functional groups into the monomer.
[0080] The refractive indices of polyacetylenic selenide compounds P1-P2, P4, P6, and P8-P9 prepared in Examples 1-2, 4, 6, and 8-9 are as follows: Figure 5 The polyacetylenic selenide compound has a high refractive index, indicating that this type of polymer has potential application value in the field of optics.
[0081] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A polyacetylenic selenide compound, characterized in that, The polyacetylenic selenide compounds have the following general structural formula: ； Where n is an integer between 2 and 400, and R is one of alkyl, substituted or unsubstituted aromatic groups.
2. The polyacetylenic selenide compound according to claim 1, characterized in that, The polyacetylenic selenide compound is selected from one of the following compounds: 、 、 、 、 。 3. The method for preparing the polyacetylenic selenide compound according to claim 1 or 2, characterized in that, Includes the following steps: 1,2-benzisexazole-3(2H)-one compounds and aromatic diyne compounds were polymerized in dichloromethane under the catalysis of silver nitrate and ammonia. After the reaction was completed, the polyyne selenide compounds were obtained through post-treatment.
4. The preparation method according to claim 3, characterized in that, The aromatic diyne compound is selected from one of the following structural formulas: 。 5. The preparation method according to claim 3, characterized in that, The 1,2-benzisoselenazole-3(2H)-ketone compound is selected from one of the following structural formulas: 。 6. The preparation method according to claim 4 or 5, characterized in that, The molar ratio of the 1,2-benzisexazole-3(2H)-one compound to the aromatic diyne compound is 1:1 to 1.
5.
7. The preparation method according to claim 6, characterized in that, The concentration of the aromatic diyne compound in dichloromethane is 0.05~1.00 mol / L; The molar ratio of silver nitrate to 1,2-benzisoselenazole-3(2H)-one compounds is 0.1~0.5:1; the molar ratio of ammonia to 1,2-benzisoselenazole-3(2H)-one compounds is 2~5:
1.
8. The preparation method according to claim 3 or 7, characterized in that, The polymerization reaction is carried out under stirring conditions, with a stirring speed of 200~500 rpm; the polymerization temperature is 0~60℃, and the reaction time is 0.5~12h.
9. The preparation method according to claim 3, characterized in that, The post-processing steps are as follows: after the reaction is completed, the reaction solution is cooled, diluted with 1 to 4 times the volume of dichloromethane, and then the diluted solution is dropped into a settling agent for sedimentation. The precipitate is collected and dried at 40 to 60°C to constant weight. The settling agent is methanol or a mixed solution of methanol and saturated saline solution.
10. The use of the polyacetylenic selenide compound according to claim 1 or 2 in refractive materials.