A thiourea-selenourea random copolymer, a preparation method and application thereof

Abstract

The application provides a thiourea-selenourea random copolymer and a preparation method and application thereof, and belongs to the technical field of polymer synthesis. The thiourea-selenourea random copolymer is synthesized by using polysaccharide, isonitrile compound and binary amine to carry out a multi-component polymerization reaction under a catalyst-free condition, and contains thiourea and selenourea repeating units. The raw materials used in the method are easy to obtain or simple to prepare. The method has the advantages of mild reaction conditions, simple process, high efficiency and high yield, and can realize efficient synthesis of the thiourea-selenourea random copolymer. The thiourea-selenourea random copolymer prepared by the application contains both sulfur atoms and selenium atoms, and thus has a high refractive index in a thin film state and has a wide application prospect in the field of light shielding materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer synthesis, and particularly relates to a thioureum-selenoureum random copolymer and a preparation method and application thereof. BACKGROUND

[0002] Selenium has higher conductivity than sulfur, and doping selenium or replacing part of sulfur in a sulfur-containing polymer can achieve unexpected performance improvement. For example, in an organic Li-S battery, doping selenium can inhibit the "shuttle effect" in the Li-S battery. Sulfur and selenium-containing polymers have excellent application prospects in the fields of Li-S / Na-S batteries, organic solar cells, organic semiconductors, high-refractive-index materials, dynamic reversible materials, biomedical materials, and the like. However, there are very limited methods for synthesizing sulfur and selenium-containing polymers at present, mainly including the following methods: (1) first synthesizing a polythiophene / selenophene monomer, and then synthesizing a conjugated polymer through Stille coupling or electrochemical synthesis for use in the fields of solar cells or organic semiconductors; (2) mixing elemental selenium and sulfur through a doping concept, and adjusting the selenium-sulfur ratio for use in Li-S / Na-S battery electrode materials; (3) synthesizing a sulfur / selenium solid solution, and then synthesizing a sulfur and selenium-containing anti-thio product through thio-alkene reaction; and (4) exchanging a dynamic disulfide bond with a diselenide bond to synthesize a sulfur and selenium-containing polymer with a dynamic bond for use in the field of dynamic materials. In the above synthesis methods, only method (1) can obtain a sulfur and selenium-containing polymer with a clear structure, but the reaction process is complex, the reaction conditions are harsh, and usually, a highly toxic organotin reagent needs to be converted from thiophene or selenophene, and the product is usually an oligomer. Although the latter methods avoid the use of organotin reagents, the reaction conditions need to be carried out at high temperature, and the obtained polymer structure is complex and difficult to characterize. The above synthesis methods seriously restrict the development of sulfur and selenium-containing polymers. SUMMARY

[0003] The present application aims to provide a thioureum-selenoureum random copolymer and a preparation method and application thereof, and solve the problems of complicated steps and high cost in synthesizing sulfur and selenium-containing polymers at present.

[0004] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0005] The present application provides a preparation method of a thioureum-selenoureum random copolymer, including the following steps:

[0006] Mixing a sulfur selenide, an isonitrile compound, and a diamine with an organic solvent, and performing a polymerization reaction in a protective atmosphere to obtain a thioureum-selenoureum random copolymer.

[0007] The sulfur selenide is selenium disulfide or selenium sulfide.

[0008] Preferably, the isonitrile compound has a structure shown in formula 1.

[0009]

[0010] In formula 1, R 1 is aryl or aliphatic.

[0011] Preferably, the R 1 is

[0012] Preferably, the diamine has a structure shown in formula 2 or formula 3:

[0013]

[0014] The R 2 includes:

[0015]

[0016] Preferably, when the sulfur selenium compound is diselenide, the molar ratio of the diselenide, the isonitrile compound and the diamine is 2.0-2.3:3.0:3.0; when the sulfur selenium compound is selenium sulfide, the molar ratio of the selenium sulfide, the isonitrile compound and the diamine is 1.0-1.2:1:1.

[0017] Preferably, the protective atmosphere includes nitrogen and / or argon; the organic solvent includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone, tetrahydrofuran, dichloromethane and trichloromethane.

[0018] Preferably, the concentration of the isonitrile compound in the organic solvent is 0.25-1 mol / L.

[0019] Preferably, the temperature of the polymerization reaction is 25-100℃, and the time is 1-12 h.

[0020] The application provides a thiourea-selenourea random copolymer prepared by the preparation method.

[0021]

[0022]

[0023] In formula I, m:n = 1-2.2:1; in formula II, x:y = 1-2.2:1.

[0024] The application provides application of the thiourea-selenourea random copolymer in the field of light-shielding materials.

[0025] The application provides a preparation method of a thioureum-selenoureum random copolymer.

[0026] The reaction raw material used in the preparation method is easy to obtain (commercially available) or simple to prepare; the method has mild reaction conditions, simple process, high efficiency and high yield, and can realize efficient synthesis of the thioureum-selenoureum random copolymer, and solves the problems of complicated steps and high cost in the synthesis of the polymer containing sulfur and selenium at the same time.

[0027] The preparation method has strong group tolerance, and various functional groups (such as ether groups, sulfide groups, aliphatic groups or aromatic rings) can be introduced into the monomer through the binary amine and isonitrile compound.

[0028] The thioureum-selenoureum random copolymer prepared by the method contains sulfur atoms and selenium atoms at the same time, and thus has a high refractive index in a thin film state, and has a wide application prospect in the field of light shielding materials. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 It is a synthesis route and nuclear magnetic spectrum of the polymer P1;

[0030] Figure 2 It is an X-ray photoelectron spectrum of the polymer P1; A is an S2p and Se 3p orbital electron X-ray photoelectron spectrum of the polymer P1, and B is an S2p and Se 3d orbital electron X-ray photoelectron spectrum of the polymer P1;

[0031] Figure 3 It is a nuclear magnetic hydrogen spectrum of the polymer P2;

[0032] Figure 4 It is a nuclear magnetic carbon spectrum of the polymer P2;

[0033] Figure 5 It is a nuclear magnetic hydrogen spectrum of the polymer P3;

[0034] Figure 6 It is a nuclear magnetic carbon spectrum of the polymer P3;

[0035] Figure 7 It is a refractive index and wavelength correlation diagram of a spin coating film prepared from the copolymer P1. DETAILED DESCRIPTION

[0036] In the application, if no special description is given, the required preparation raw materials or reagents are all commercially available goods which are well known to those skilled in the art.

[0037] The application provides a preparation method of a thioureum-selenoureum random copolymer, which comprises the following steps:

[0038] The thioureum-selenoureum random copolymer is obtained by mixing a thiuramyl selenide, an isonitrile compound and a diamine with an organic solvent and performing a polymerization reaction in a protective atmosphere.

[0039] The thiuramyl selenide is preferably SeS2.

[0040] In the application, the isonitrile compound preferably has the structure shown in formula 1.

[0041]

[0042] In formula 1, R 1 is an aryl group or an aliphatic group.

[0043] In the application, the R 1 is preferably The isonitrile compound preferably corresponds to

[0044]

[0045] In the application, the diamine preferably has the structure shown in formula 2 or formula 3.

[0046]

[0047] The R 2 comprises:

[0048]

[0049] In the application, the diamine is preferably

[0050]

[0051]

[0052] In the application, when the thiuramyl selenide is SeS2, the molar ratio of the SeS2, the isonitrile compound and the diamine is 2.0-2.3:3.0:3.0, and more preferably 2.22:3; when the thiuramyl selenide is SeS, the molar ratio of the SeS, the isonitrile compound and the diamine is 1.0-1.2:1:1.

[0053] In the application, the protective atmosphere preferably comprises nitrogen and / or argon.

[0054] In the present application, the organic solvent preferably includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dichloromethane and trichloromethane, and more preferably dimethyl sulfoxide (DMSO); when the organic solvent is two or more of the above, the present application does not have a special limitation on the ratio of different kinds of organic solvents, and any ratio is acceptable.

[0055] In the present application, the concentration of the isonitrile compound in the organic solvent is preferably 0.25-1 mol / L, more preferably 0.25-0.5 mol / L, and further preferably 0.25 mol / L.

[0056] In the present application, the temperature of the polymerization reaction is preferably 25-100°C, more preferably 50-90°C, and further preferably 60-80°C; the time is preferably 1-12 h, more preferably 8-12 h; and the polymerization reaction is preferably carried out under stirring, and the stirring speed is preferably 200-600 rpm, more preferably 300-500 rpm, and further preferably 400 rpm.

[0057] After the polymerization reaction is completed, the present application preferably precipitates the obtained product liquid in methanol, filters and dries to obtain a thiourea-selenourea random copolymer.

[0058] The present application provides a thiourea-selenourea random copolymer prepared by the preparation method described in the above technical solution, which has a structure shown in Formula I or Formula II:

[0059]

[0060] In Formula I, m:n = 1-2.2:1; and in Formula II, x:y = 1-2.2:1.

[0061] In the present application, more preferably, m:n = 2:1.

[0062] In the present application, the thiourea-selenourea random copolymer preferably has a structure shown in Formula I or Formula II.

[0063]

[0064] The present application provides an application of the thiourea-selenourea random copolymer described in the above technical solution in the field of light-shielding materials.

[0065] The technical solutions provided by the present application will be described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0066] Example 1

[0067] A thiourea-selenourea random copolymer has a structure shown in P1, and a reaction formula is shown in Formula (1):

[0068]

[0069] wherein, selenium disulfide 1 was purchased from Macklin Chemicals, isonitrile 2 was synthesized according to the literature (JACS, 2018, 140:6156), 3a was purchased from ANPEL Scientific Instruments Co., Ltd.

[0070] The synthesis steps of the thioureaseleurea random copolymer are as follows: take selenium disulfide 1 (52.5 mg, 0.37 mmol), isonitrile 2 (78.2 mg, 0.50 mmol), diamine 3a (99.1 mg, 0.50 mmol) in a polymerization tube with a magnet, replace the gas three times, nitrogen as protective gas, add 2 mL of anhydrous DMSO, heat to 80℃, stop stirring at 400 rpm after 12h, add 5 mL of DMSO dilution, filter the reaction liquid through a dropper with cotton, then add it to 120 mL of methanol and stir vigorously, a large amount of white precipitate is precipitated, after standing, filter, wash the precipitate with methanol (3x50 mL) and dry to obtain a white solid, molecular weight M w = 236300 g / mol, M w / M n = 2.95, yield 97%.

[0071] The structure is described in detail taking P1 as an example:

[0072] Figure 2 is the X-ray photoelectron spectrum of polymer P1, wherein A is the S2p and Se 3p orbital electron X-ray photoelectron spectrum of polymer P1, B is the S2p and Se 3d orbital electron X-ray photoelectron spectrum of polymer P1, and C is the Se 3p orbital electron X-ray photoelectron spectrum of polymer P1. Figure 1 It can be seen that the S2p orbital electron binding energy is 162.10 / 163.33, the Se 3p orbital electron binding energy is 161.17 / 166.57, and by envelope fitting, it can be known that the molar ratio of S and Se is 2:1.

[0073] The nuclear magnetic resonance spectrum of the thioureaseleurea random copolymer prepared in this example is shown in Figure 1 , and the nuclear magnetic resonance data is:

[0074] 1 H NMR (600 MHz, d6-DMSO) δ 9.93 (s, 1H), 9.52 (s, 1H), 8.42 (s, 1H), 8.07 (s, 1H), 7.31-7.27 (m, 5H), 7.21-7.18 (m, 5H), 4.85-4.55 (m, 4H), 3.86 (d, J = 4.9 Hz, 2H).

[0075] 13C NMR (150 MHz, d6-DMSO) δ 180.72, 179.23, 138.59, 137.65, 137.49, 137.30, 137.04, 136.32, 129.29, 128.91, 127.37, 127.31, 124.64, 123.70, 49.90, 47.01. 77 Se NMR (114 MHz, d6-DMSO) δ 211.07. Elemental analysis (C, N, S, H): Calc. C 61.36%, N 12.45%, S 9.50%, H 5.00%, Found C 61.15%, N 12.30%, S 8.51%, H 5.10%.

[0076] Example 2

[0077] A thioureaseleloureum random copolymer compound, whose structural formula is shown as P2, and the reaction formula is shown as formula (2):

[0078]

[0079] The synthesis steps of the thioureaseleloureum random copolymer are as follows: take selenium disulfide 1 (52 mg, 0.37 mmol), isonitrile 2 (78 mg, 0.50 mmol), and diamine 3b (181 mg, 0.50 mmol) in a polymerization tube with a magnet added, exchange gas three times, nitrogen as protective gas, add 2 mL of anhydrous DMSO, heat to 80°C, 400 rpm stirring reaction for 8 h, then stop, add 5 mL of DMSO for dilution, filter the reaction liquid through a dropper with cotton, and then drop into 120 mL of methanol and stir vigorously, a large amount of white precipitate is precipitated, after standing, suction filtration, the precipitate is washed with methanol (3 x 50 mL) and dried to obtain a white solid, yield 99%, molecular weight M w = 208100 g / mol, M w / M n = 1.97.

[0080] The nuclear magnetic resonance spectrum of the thioureaseleloureum random copolymer prepared in this example is shown in Figure 3 and Figure 4 , and the nuclear magnetic data are:

[0081] 1 H NMR (600 MHz, d6-DMSO) δ 9.92 (s, 0.5H), 9.52 (s, 1H), 8.38 (s, 0.5H), 8.07 (s, 1H), 7.44-7.30 (m, 8H), 7.01-6.98 (m, 4H), 4.87-4.73 (m, 4H).

[0082] 13 C NMR (150 MHz, DMSO) δ 181.03 (C=S), 179.77 (C=Se), 154.52, 153.53, 153.17, 137.60, 134.70, 127.74, 127.30, 127.25, 126.85, 126.80, 125.64, 125.64, 120.85, 120.70, 118.89, 118.62, 116.63, 114.86, 49.85, 46.97.

[0083] Example 3

[0084] A thioureaseleloureum random copolymer, whose structural formula is shown as P3, and the reaction formula is shown as formula (3):

[0085]

[0086] The synthesis steps of the thioureaseleloureum random copolymer are as follows: take selenium disulfide 1 (52 mg, 0.37 mmol), isonitrile 2 (78 mg, 0.50 mmol), and diamine 3c (100 mg, 0.50 mmol) in a polymerization tube with a magnet added, exchange the gas three times, nitrogen as the protective gas, add 2 mL of anhydrous DMSO, warm to 80°C, and stop stirring at 400 rpm after 8 h of reaction. Add 5 mL of DMSO for dilution, filter the reaction liquid through a dropper with cotton, and then drop it into 120 mL of methanol and stir vigorously. A large amount of white precipitate is precipitated, and after standing, it is suction filtered. The precipitate is washed with methanol (3 x 50 mL) and dried to obtain a white solid with a yield of 99%, a molecular weight M w = 208100 g / mol, M w / M n = 1.97.

[0087] The nuclear magnetic resonance chart of the thioureaseleloureum random copolymer prepared in this example is shown in Figures 5-6 , and the nuclear magnetic resonance data is:

[0088] 1 H NMR (600 MHz, d6-DMSO) δ 9.92 (s, 0.5H), 9.52 (s, 1H), 8.38 (s, 0.5H), 8.07 (s, 1H), 7.44-7.30 (m, 8H), 7.01-6.98 (m, 4H), 4.87-4.73 (m, 4H).

[0089] 13C NMR (150 MHz, DMSO) δ 181.03 (C=S), 179.77 (C=Se), 154.52, 153.53, 153.17, 137.60, 134.70, 127.74, 127.30, 127.25, 126.85, 126.80, 125.64, 125.64, 120.85, 120.70, 118.89, 118.62, 116.63, 114.86, 49.85, 46.97.

[0090] Application Example

[0091] The polymer P1 prepared in Example 1 was dissolved in N,N-dimethylacetamide solvent to prepare a solution with a mass fraction of 40%, 60 μL of which was uniformly spread on a 2x2 cm single-throw silicon wafer to prepare a P1 film by a spin coater at a speed of 1200 r / min for 30 s. The refractive index of the film was tested by an ellipsometer, and the results are shown in Table 1. Figure 7 .

[0092] Figure 7 The results show that the refractive index of the prepared copolymer film at 633 nm is 1.7505, which is much higher than that of a commercially available bisphenol A polycarbonate (PC) material (the refractive index of bisphenol A polycarbonate at 589 nm is 1.586), and the copolymer has application potential in high-refractive-index materials and is expected to be used in the field of optical devices. Therefore, the copolymer P1 has a high refractive index, which is due to the simultaneous presence of sulfur atoms and selenium atoms in the thiourease-selenourease random copolymer, so that the polymer exhibits a high refractive index in a film state.

[0093] As can be seen from the above examples, the thiourease-selenourease random copolymer is synthesized by using a sulfur selenide, an isonitrile and a binary amine to perform a multi-component polymerization reaction in a strong polar solvent; the method avoids the use of dangerous reagents and scarce reagents, and has a high yield and is easy to operate; the copolymer has application potential in high-refractive-index materials and is expected to be used in the field of optical devices.

[0094] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for preparing a random thiourea-selenourea copolymer, characterized by, The method comprises the following steps: mixing a sulfur-selenium compound, an isonitrile compound and a diamine with an organic solvent, and performing a polymerization reaction in a protective atmosphere to obtain a thiourea-selenourea random copolymer; the sulfur-selenium compound is selenium disulfide or selenium sulfide; the isonitrile compound has a structure shown in formula 1: Formula 1; In formula 1, R 1 is an aryl or aliphatic group; the diamine has a structure shown in formula 2 or formula 3: Formula 2; Formula 3; The R 2 comprises: , , , , , , or ; when the sulfur-selenium compound is selenium disulfide, the molar ratio of the selenium disulfide, the isonitrile compound and the diamine is 2.0-2.3:3.0:3.0; when the sulfur-selenium compound is selenium sulfide, the molar ratio of the selenium sulfide, the isonitrile compound and the diamine is 1.0-1.2:1:1; the temperature of the polymerization reaction is 25-100 DEG C.

2. The production method according to claim 1, characterized by, The R 1 is , , or .

3. The production method according to claim 1, characterized by, the protective atmosphere used in the protective atmosphere comprises nitrogen and / or argon; and the organic solvent comprises one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dichloromethane and trichloromethane.

4. The production method according to claim 1 or 3, characterized by, the concentration of the isonitrile compound in the organic solvent is 0.25-1 mol / L.

5. The preparation method according to claim 1, characterized in that, the polymerization reaction is performed for 1-12 hours.

6. The thiourea-selenourea random copolymer prepared by the method of any one of claims 1 to 5, characterized in that, has a structure shown in formula I or formula II: Formula I; Formula II; in formula I, m:n = 1-2.2:1; and in formula II, x:y = 1-2.2:

1.

7. Application of the thiourea-selenourea random copolymer of claim 6 in the field of light-shielding materials.

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