Sulfur-containing compound and sulfur-containing polymer as well as preparation method and application thereof

Abstract

The invention discloses a sulfur-containing compound and a sulfur-containing polymer as well as a preparation method and application of the sulfur-containing compound and the sulfur-containing polymer. Under the catalysis of alkali, a poly (1, 2, 4-thiadiazole) compound, a poly (amidino-thiourea) compound, 1, 2, 4-thiadiazole and amidino-thiourea small molecules are respectively synthesized by changing the reaction atmosphere and raw materials. The method disclosed by the invention is mild in reaction condition, simple to operate, green, economical, energy-saving and environment-friendly, and has the characteristics of high reaction efficiency, high atom economy and high regioselectivity. And the synthesized poly (1, 2, 4-thiadiazole) compound and poly (amidino-thiourea) compound have good thermal stability, good film-forming property, excellent thermal stability and relatively high refractive index, and have potential application values in the fields of optics and photoelectrons.

Description

Technical Field

[0001] The present invention belongs to the fields of organic chemistry, polymer chemistry and materials technology, and in particular relates to a sulfur-containing compound and a sulfur-containing polymer, and a preparation method and application thereof. Background Art

[0002] Sulfur-containing heterocyclic polymers, including polythiophene, polythiazole, polybenzothiazole, and poly(1,3,4-thiadiazole), are widely used in solar cells, thermoelectric materials, and luminescent materials due to their conjugated structures. Elemental sulfur, a common sulfur resource, is not only low-cost but also widely applicable in industrial production, resulting in polymers exhibiting excellent mechanical properties and processability. A literature review revealed that the synthesis of polythiazole, polybenzothiazole, and poly(1,3,4-thiadiazole) is primarily limited by the use of metal catalysts, heterocyclic monomers, and cumbersome synthesis steps. However, the reported synthesis methods for poly(1,2,4-thiadiazole) polymers are limited, significantly hindering their development and application. Furthermore, a series of poly(guanyl-thioureas) have been successfully prepared under nitrogen. By controlling the reaction gas environment, guanyl-thioureas and 1,2,4-thiadiazoles were efficiently and economically synthesized via multicomponent reactions in both nitrogen and air environments.

[0003] The reported method of polythiourea still has certain shortcomings, which hinders the development of this type of polymer. The synthesis method of polythiourea is shown in formula (1). The method uses elemental sulfur, isonitrile and amine compounds to synthesize polythiourea, but it is not possible to synthesize polythiourea with rich hydrogen bonds. As we all know, hydrogen bonds are a kind of intermolecular force that is widely present in nature. The introduction of multiple hydrogen bonds in polymer structure design has received attention from many researchers. The groups currently used to construct hydrogen bonds are mainly amide groups, urea groups and thiourea groups. Researchers can significantly enhance the mechanical properties and self-healing properties of polymer materials by introducing these groups, and obtain materials for wearable electronic devices, marine protective coatings, etc.

[0004]

[0005] The synthesis of poly(1,2,4-thiadiazole) often uses a coupling reaction strategy, using metal catalysts and thiazole monomers. The reaction time is long, the synthesized polymer structures are limited, and the characterization is unclear (Bryton R. Varju, Alan J. Lough, Dwight S. Seferos. Investigating the Degradability and Optoelectronic Properties of π-Conjugated Polymers with 1,2,4-Chalcogenadiazole Linkers. Macromolecules, 2025, 58, 1214-1222.). Summary of the Invention

[0006] In order to address the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing poly(1,2,4-thiadiazole) and poly(guanyl-thiourea), guanyl-thiourea and 1,2,4-thiadiazole small molecules.

[0007] Another object of the present invention is to provide two types of polymers: poly (1,2,4-thiadiazole) compounds and poly (guanyl-thiourea) compounds.

[0008] Another object of the present invention is to provide applications of poly(1,2,4-thiadiazole) compounds and poly(guanyl-thiourea) compounds, which are materials with relatively high refractive index.

[0009] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0010] A method for preparing a sulfur-containing compound and a sulfur-containing polymer, wherein the sulfur-containing polymer comprises a poly(1,2,4-thiadiazole) compound and a poly(guanyl-thiourea) compound; and the sulfur-containing compound comprises guanylthiourea and 1,2,4-thiadiazole.

[0011] (1) The preparation method of the poly (1,2,4-thiadiazole) compound comprises the following steps:

[0012] In an oxidizing atmosphere, elemental sulfur, a polyisocyanide compound, a polyamide compound, and a base compound are added to an organic solvent to obtain a mixed solution, and the mixture is heated under stirring to perform a polymerization reaction to obtain a poly(1,2,4-thiadiazole) compound;

[0013] (2) The preparation method of the poly(amidino-thiourea) compound comprises the following steps:

[0014] Under a protective atmosphere, elemental sulfur, a polyisocyanide compound, a polyamide compound, and a base compound are added to an organic solvent to obtain a mixed solution, and the mixture is heated under stirring to perform a polymerization reaction to obtain a poly(amidino-thiourea) compound;

[0015] (3) The preparation method of the 1,2,4-thiadiazole comprises the following steps:

[0016] Under an oxidizing atmosphere, elemental sulfur, an isonitrile compound, an amide compound, and a base compound are added to an organic solvent to obtain a mixed solution, and the mixture is heated under stirring to react to obtain a sulfur-containing compound 1,2,4-thiadiazole; the isonitrile compound includes a monobasic isonitrile compound and a polybasic isonitrile compound, the amide compound includes a monobasic amide compound and a polybasic amide compound, and at least one of the isonitrile compound and the amide compound is a monobasic compound;

[0017] (4) The preparation method of the guanyl-thiourea comprises the following steps:

[0018] Under a protective atmosphere, elemental sulfur, an isocyanide compound, an amide compound and an alkaline compound are added to an organic solvent to obtain a mixed liquid, which is then heated under stirring to react to obtain a sulfur-containing compound guanyl-thiourea; the isocyanide compound includes a monobasic isocyanide compound and a polybasic isocyanide compound, the amide compound includes a monobasic amide compound and a polybasic amide compound, and at least one of the isocyanide compound and the amide compound is a monobasic compound.

[0019] Preferably, the structural formula of the poly (1,2,4-thiadiazole) compound is one of the following general structural formulas:

[0020]

[0021] The structural formula of the poly(amidino-thiourea) compound is one of the following general structural formulas:

[0022]

[0023] The general structural formulas of the guanyl-thiourea and 1,2,4-thiadiazole are respectively

[0024] Wherein, n is an integer between 2 and 400; R 1 、R 2 、R 3 、R 4 are independently selected from organic groups.

[0025] More preferably, R 1 、R 2 、R 3 、R 4 are independently selected from aryl or alkyl.

[0026] More preferably, the R 1 、R 2 is one of the following substituent groups:

[0027]

[0028] The R 3 、R 4 is one of the following substituent groups:

[0029]

[0030] Preferably, the polybasic isocyanide compound is a dibasic isocyanide compound, the polybasic amide compound is a dibasic amide compound; and the amide compound is amide hydrochloride.

[0031] Further preferably, the diamide compound comprises the following structural formula:

[0032]

[0033] Further preferably, the binary isonitrile compound comprises the following structural formula:

[0034]

[0035] Further preferably, the monoamide compound comprises the following structural formula:

[0036] Further preferably, the monobasic isonitrile compound comprises the following structural formula:

[0037]

[0038] Preferably, the base compound in methods (1), (2), (3) and (4) comprises one or more of triethylamine, N,N-diisopropylethylamine, potassium carbonate, cesium carbonate, triethylenediamine and sodium carbonate;

[0039] Preferably, the organic solvent in methods (1), (2), (3) and (4) is one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, acetonitrile, 1,4-dioxane, tetrahydrofuran and 1,2-dichloromethane;

[0040] Preferably, the molar ratio of elemental sulfur, polyisocyanide compound, polyamide compound and base compound in methods (1) and (2) is 2-8:1:1:1.5-8;

[0041] Preferably, the molar ratio of elemental sulfur, isonitrile compound, amide compound and base compound in methods (3) and (4) is 2-8:1:1:1.5-8.

[0042] Preferably, the concentration of the polyamide compound in the mixed solution in methods (1) and (2) is 0.05 to 1 mol / L; the concentration of the amide compound in the mixed solution in method (3) is 0.05 to 1 mol / L;

[0043] Preferably, the reaction temperature in methods (1), (2), (3) and (4) is 25 to 120° C., and the reaction time is 0.5 to 8 h.

[0044] Preferably, the oxidizing atmosphere in method (1) is an air atmosphere; and the protective atmosphere in methods (2) and (4) is an inert atmosphere.

[0045] Preferably, after the reaction in methods (1) and (2) is completed, the reaction mother liquor is dissolved in an organic solvent, and then added to a precipitant for precipitation, the precipitate is collected, and dried to constant weight; the precipitant comprises one or more of methanol, n-hexane and ethanol; and the drying temperature is 20 to 30°C.

[0046] Preferably, after the reaction in methods (3) and (4) is completed, water is added to quench the reaction, and the mixture is extracted with ethyl acetate. The organic phases are combined, and the solvent is removed by vacuum rotary evaporation to obtain a crude product, which is purified by silica gel column chromatography using petroleum ether / ethyl acetate as an eluent.

[0047] The sulfur-containing compound and sulfur-containing polymer prepared by the above preparation method.

[0048] The above-mentioned sulfur-containing compounds and sulfur-containing polymers are used in the fields of optics and optoelectronics, especially in the preparation of light-emitting electrochemical cells, optical waveguides, infrared reflective coatings, anti-reflective coatings, CMOS image sensors and infrared thermal imaging materials.

[0049] The present invention prepares two polymers, poly(1,2,4-thiadiazole) compounds and poly(guanyl-thiourea) compounds, respectively, under different air and nitrogen atmospheres. The invention introduces guanyl groups into polythiourea to produce poly(guanyl-thiourea)s with multiple hydrogen bonds, providing new applications for sulfur-containing polymers. The structures of the poly(1,2,4-thiadiazole) compounds and poly(guanyl-thiourea) compounds synthesized in the present invention have not been reported. The synthesis of these two types of polymers will greatly enrich the variety of sulfur-containing polymers and facilitate the exploration of their chemical properties and research into their applications.

[0050] Beneficial effects of the present invention:

[0051] (1) The present application prepares two types of novel polymers, poly(1,2,4-thiadiazole) compounds and poly(amidino-thiourea) compounds. Among them, the aromatic heterocyclic polymer poly(1,2,4-thiadiazole) and the poly(amidino-thiourea) with rich hydrogen bonds are both conducive to improving the refractive index performance of the polymer.

[0052] (2) In the preparation method of the present application, the polymerization conditions are mild, green and economical, the process is simple, the polymerization efficiency is high, the atomic utilization rate is high, and the regioselectivity is good.

[0053] (3) In the preparation method of the present application, the polymerization reaction does not require a metal catalyst, and sulfur elements can be introduced into the polymer in a simple manner.

[0054] (4) In the preparation method of the present application, the substrate group has strong resistance, and various functional groups can be introduced into the monomer.

[0055] (5) The poly(1,2,4-thiadiazole) compounds and poly(amidino-thiourea) compounds prepared by the present application both have high thermal stability.

[0056] (6) The poly(1,2,4-thiadiazole) compounds and poly(amidino-thiourea) compounds prepared by the present application both have good film-forming properties, and the introduction of sulfur atoms makes them have a high refractive index, which has potential application value in the fields of optics and optoelectronics.

[0057] (7) The small molecule reaction conditions of the present application are mild, green and economical, and the yield is relatively high. BRIEF DESCRIPTION OF DRAWINGS

[0058] Figure 1 The nuclear magnetic resonance hydrogen spectrum comparison chart of the poly(1,2,4-thiadiazole) compound prepared in Example 1 of the present application, its corresponding monomer and model compound in deuterated DMSO;

[0059] Figure 2 The nuclear magnetic resonance carbon spectrum comparison chart of the poly(1,2,4-thiadiazole) compound prepared in Example 1 of the present application, its corresponding monomer and model compound in deuterated DMSO;

[0060] Figure 3 The nuclear magnetic resonance hydrogen spectrum comparison chart of the poly(amidino-thiourea) compound prepared in Example 6 of the present application, its corresponding monomer and model compound in deuterated DMSO;

[0061] Figure 4 The nuclear magnetic resonance carbon spectrum comparison chart of the poly(amidino-thiourea) prepared in Example 6 of the present application, its corresponding monomer and model compound in deuterated DMSO;

[0062] Figure 5The infrared absorption spectra of the poly (1,2,4-thiadiazole) compound and its corresponding monomer and model compound prepared in Example 1 of the present invention;

[0063] Figure 6 The infrared absorption spectra of the poly(amidino-thiourea) compound prepared in Example 6 of the present invention and its corresponding monomer and model compound;

[0064] Figure 7 This is a thermogravimetric curve of the poly (1,2,4-thiadiazole) compound prepared in Example 1 of the present invention;

[0065] Figure 8 This is a thermogravimetric curve of the poly(amidino-thiourea) compound prepared in Example 6 of the present invention;

[0066] Figure 9 This is a refractive index diagram of the film of the poly (1,2,4-thiadiazole) compound prepared in Example 1 of the present invention.

[0067] Figure 10 This is a refractive index diagram of the film of the poly(amidino-thiourea) compound prepared in Example 6 of the present invention. DETAILED DESCRIPTION

[0068] The following examples further illustrate the specific implementation of the present invention, but the implementation and protection of the present invention are not limited thereto. It should be noted that if there are any processes not specifically described below, they can be implemented or understood by those skilled in the art with reference to the prior art. If the manufacturer of the reagents or instruments used is not indicated, they are deemed to be conventional products that can be purchased commercially.

[0069] The present invention provides a poly (1,2,4-thiadiazole) and a poly (amidino-thiourea) compound, wherein the poly 1,2,4-thiadiazole compound comprises the following general structural formula:

[0070]

[0071] The structural formula of the poly (amidino-thiourea) polymer is one of the following general structural formulas:

[0072]

[0073] Wherein, n is an integer between 2 and 400; R 1 、R 2 are independently selected from aryl or alkyl.

[0074] The general structural formulas of the guanyl-thiourea and 1,2,4-thiadiazole are respectively

[0075] R 3 、R 4independently selected from aryl or alkyl.

[0076] The present application provides poly(1,2,4-thiadiazole) and poly(amidino-thiourea) compounds and a preparation method, comprising the following steps:

[0077] (1) under air or a protective atmosphere, elemental sulfur, isonitrile, amide hydrochloride and a base are added into an organic solvent to obtain a mixed solution, and a polymerization reaction is carried out under stirring and heating to obtain a reaction mother liquor;

[0078] (2) the reaction mother liquor obtained in step (1) is dissolved in an organic solvent, and then is added to a precipitant to perform precipitation, and the precipitate is collected and dried to constant weight to obtain the poly(1,2,4-thiadiazole) polymer and the poly(amidino-thiourea) polymer respectively.

[0079] The present application provides an amidino-thiourea compound and a preparation method thereof, comprising the following steps:

[0080] (1) under a protective atmosphere, elemental sulfur, isonitrile (monomer or dimer), amide hydrochloride (monomer) and a base are added into an organic solvent to obtain a mixed solution, and a reaction is carried out under stirring at room temperature to obtain a reaction mother liquor;

[0081] (2) after the reaction is completed, water is added to quench the reaction, and ethyl acetate is used for extraction three times, and the organic phase is combined, and the solvent is removed by vacuum rotary evaporation to obtain a crude product. The crude product is purified by silica gel column chromatography with petroleum ether / ethyl acetate as an eluent to obtain the amidino-thiourea compound.

[0082] The present application provides a 1,2,4-thiadiazole compound and a preparation method thereof, comprising the following steps:

[0083] (1) under an air atmosphere, elemental sulfur, isonitrile (monomer or dimer), amide hydrochloride (monomer) and a base are added into an organic solvent to obtain a mixed solution, and a reaction is carried out under stirring and heating to obtain a reaction mother liquor;

[0084] (2) after the reaction is completed, water is added to quench the reaction, and ethyl acetate is used for extraction three times, and the organic phase is combined, and the solvent is removed by vacuum rotary evaporation to obtain a crude product. The crude product is purified by silica gel column chromatography with petroleum ether / ethyl acetate as an eluent to obtain the 1,2,4-thiadiazole compound.

[0085] Further, the dimer amide hydrochloride compound specifically comprises the following structural formula:

[0086]

[0087] Further, the dimer isonitrile compound comprises the following structural formula:

[0088] Further, the dimer isonitrile compound comprises the following structural formula:

[0089] Furthermore, the monoamide compound specifically comprises the following structural formula:

[0090]

[0091] Furthermore, the monobasic isonitrile compound comprises the following structural formula:

[0092]

[0093] Furthermore, the base compound comprises one or more of triethylamine, N,N-diisopropylethylamine, potassium carbonate, cesium carbonate, triethylenediamine and sodium carbonate;

[0094] Furthermore, the organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, acetonitrile, 1,4-dioxane, tetrahydrofuran and 1,2-dichloromethane.

[0095] Furthermore, the precipitant comprises one or more of methanol, n-hexane and ethanol.

[0096] Furthermore, the molar ratio of elemental sulfur, isonitrile, diamide hydrochloride and base is 2-8:1:1:1.5-8.

[0097] Furthermore, the concentration of the organic solvent is 0.05 to 1 mol / L.

[0098] Furthermore, the temperature of the elemental sulfur, isocyanide, diamide hydrochloride and base is 25-120° C., and the reaction time is 0.5-8 h.

[0099] Furthermore, the drying temperature is 20-30°C.

[0100] In the present invention, the stirring speed is 250-800 rpm, preferably 500 rpm.

[0101] The present invention provides a poly(1,2,4-thiadiazole) and poly(guanyl-thiourea) compound, the synthesis of 1,2,4-thiadiazole and guanyl-thiourea small molecules, and the application of poly(1,2,4-thiadiazole) and poly(guanyl-thiourea) in the fields of optics and optoelectronics.

[0102] Example 1

[0103] A poly (1,2,4-thiadiazole) compound, whose structural formula is shown in P1:

[0104]

[0105] The poly (1,2,4-thiadiazole) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (2):

[0106]

[0107] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anage. M2 is 1,4-benzenedicarboxylic acid amide hydrochloride, which can be purchased from the market, in this example, purchased from Anage. M3 is 1,4-phenylbenzyl isocyanide. In this example, DBU, DIPEA, or triethylamine were all purchased from Anage.

[0108] The preparation steps of the poly (1,2,4-thiadiazole) compound are as follows:

[0109] In a 10 ml polymerization tube (air atmosphere), 1 monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 47.0 mg (0.2 mmol) of monomer M2 and 31.2 mg (0.2 mmol) of monomer M3 were added in sequence, 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10 of DIPEA was added. The mixture was reacted at 100 ° C for 2 h and stirred at a rate of 500 rpm. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20 ° C to obtain the poly (1,2,4-thiadiazole) compound P1.

[0110] The yield of the poly(1,2,4-thiadiazole) compound P1 was 80%, the weight average molecular weight was 10800 g / mol, and the molecular weight distribution was 1.40. The comparison of the H NMR spectra of the poly(1,2,4-thiadiazole) compound, its corresponding monomer, and the model compound (* represents the solvent peak) is shown in Figure 1 , the comparison of its carbon NMR spectrum is shown in the figure below Figure 2 As shown, Figure 1 The chemical shift at 8.99 ppm corresponds to the characteristic peak of hydrogen atoms on the -NH of the poly(1,2,4-thiadiazole) compound. Figure 2 The chemical shifts at 183.25 and 167.91 ppm are characteristic peaks of poly(1,2,4-thiadiazole) compounds, so it can be determined that the polymer is a poly(1,2,4-thiadiazole) compound. In addition, Figure 5 This is an infrared absorption spectrum of the poly (1,2,4-thiadiazole) compound prepared in Example 1 of the present invention, its corresponding monomer, and a model compound. Figure 7 The thermogravimetric curve of P1 is Figure 7It can be seen that the temperature corresponding to the 5% weight loss is 255°C, and it has good thermal stability. Based on the good film-forming properties and high sulfur content of the poly (1,2,4-thiadiazole) compound, P1 (30 mg) prepared in this example was dissolved in chlorobenzene, and then filtered through a 200 μm nylon filter membrane. 40 μL of the filtrate was dropped on a 2cm*2cm silicon wafer for spin coating. The selected spin coater model is KW-41, and the rotation speed is 1000 rpm. The prepared film is vacuum dried for 2 hours, and then the refractive index is tested by a variable angle spectroscopic polarimeter. The selected instrument model is Vertical VASE (V-VASE). The wavelength range is 400-1700 nm, the film thickness is 110 nm, and the results are as follows. Figure 9 As shown in the figure, it can be seen that the refractive index of the polymer at 589nm is 1.7481, which is much higher than that of common polymers (the refractive index of commercial polymer materials is mostly between 1.5 and 1.6), and has potential applications in the fields of optics and optoelectronics.

[0111] Example 2

[0112] A poly (1,2,4-thiadiazole) compound, whose structural formula is shown in P2:

[0113]

[0114] The poly (1,2,4-thiadiazole) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (III):

[0115]

[0116] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anage. M2 is 1,4-benzenedicarboxylic acid amide hydrochloride, which can be purchased from the market, and in this example, it was purchased from Anage. M4 is bis(4-isocyanophenyl)methane. In this example, DBU, DIPEA, or triethylamine were all purchased from Anage.

[0117] The preparation steps of the poly (1,2,4-thiadiazole) compound are as follows:

[0118] In a 10 ml polymerization tube (air atmosphere), monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 47.0 mg (0.2 mmol) of monomer M2 and 43.6 mg (0.2 mmol) of monomer M4 were added in sequence, 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10 mmol of DIPEA was added. The reaction was carried out at 25 ° C for 8 h. After the reaction, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20 ° C to obtain the poly (1,2,4-thiadiazole) compound P2.

[0119] After measurement and analysis, the yield of poly (1,2,4-thiadiazole) compound P2 was 78%, the weight-average molecular weight was 10000g / mol, and the molecular weight distribution was 1.43. P2 (30mg) prepared in this example was dissolved in chlorobenzene and then filtered through a 200μm nylon filter membrane. 40μL of the filtrate was dropped onto a 2cm*2cm silicon wafer for spin coating. The selected spin coater model was KW-41, with a rotation speed of 1000rpm. The prepared film was vacuum dried for 2h and then subjected to a refractive index test using a variable angle spectroscopic ellipsometry with a wavelength range of 400-1700nm and a film thickness of 138nm. The results showed that the refractive index of the polymer P2 film at 589nm was 1.8124.

[0120] Example 3

[0121] A poly (1,2,4-thiadiazole) compound, whose structural formula is shown in P3:

[0122]

[0123] The poly (1,2,4-thiadiazole) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (IV):

[0124]

[0125] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anergy. M5 is [1,1'-biphenyl]-4,4'-bis(carboximide) dihydrochloride, which can be purchased from the market, in this example, purchased from Anergy. M3 is 1,4-phenylbenzyl isocyanide. In this example, DBU, DIPEA, or triethylamine were all purchased from Anergy.

[0126] The preparation steps of the poly (1,2,4-thiadiazole) compound are as follows:

[0127] In a 10 ml polymerization tube (air atmosphere), monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 62.2 mg (0.2 mmol) of monomer M5 and 43.6 mg (0.2 mmol) of monomer M3 were added in sequence, 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10 of DIPEA was added. The reaction was carried out at 120 ° C for 0.5 h. After the reaction, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20 ° C to obtain the poly (1,2,4-thiadiazole) compound P3.

[0128] After analysis, the yield of the poly(1,2,4-thiadiazole) compound P3 was 78%, the weight-average molecular weight was 7400 g / mol, and the molecular weight distribution was 1.27. P3 (30 mg) prepared in this example was dissolved in chlorobenzene and then filtered through a 200 μm nylon filter membrane. 40 μL of the filtrate was dropwise applied to a 2 cm*2 cm silicon wafer and spin-coated. The selected spin-coating apparatus was a KW-41 model with a rotation speed of 1000 rpm. The prepared film was vacuum-dried for 2 hours and then subjected to a refractive index test using a variable-angle spectroscopic ellipsometer over a wavelength range of 400-1700 nm and a film thickness of 151 nm. The results showed that the refractive index of the polymer P3 film at 589 nm was 1.7670.

[0129] Example 4

[0130] A poly (1,2,4-thiadiazole) compound, the structural formula of which is shown in P4:

[0131]

[0132] The poly (1,2,4-thiadiazole) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (5):

[0133]

[0134] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anage. M2 is 1,4-benzenedicarboxylic acid amide hydrochloride, which can be purchased from the market, in this example, purchased from Anage. M6 is 1,4-diisocyanato-2,5-dimethylbenzene. In this example, DBU, DIPEA, or triethylamine were all purchased from Anage.

[0135] The preparation steps of the poly (1,2,4-thiadiazole) compound are as follows:

[0136] In a 10 ml polymerization tube (air atmosphere), monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 47.0 mg (0.2 mmol) of monomer M2 and 31.2 mg (0.2 mmol) of monomer M6 were added in sequence, 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10 of DIPEA was added. The reaction was carried out at 60 ° C for 4 h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20 ° C to obtain the poly (1,2,4-thiadiazole) compound P4.

[0137] Analysis revealed a yield of 86% for the poly(1,2,4-thiadiazole) compound P4, a weight-average molecular weight of 7900 g / mol, and a molecular weight distribution of 1.31. 30 mg of P4 prepared in this example was dissolved in chlorobenzene and filtered through a 200 μm nylon filter membrane. 40 μL of the filtrate was then dropwise applied to a 2 cm*2 cm silicon wafer and spin-coated. The spin coater used was a KW-41 model with a rotation speed of 1000 rpm. The prepared film was vacuum-dried for 2 hours and then subjected to refractive index testing using a variable-angle spectroscopic ellipsometer. The film thickness was 158.5 nm over a wavelength range of 400-1700 nm. The results showed a refractive index of 1.8276 at 632.8 nm for the polymer P4 film.

[0138] Example 5

[0139] A poly (1,2,4-thiadiazole) compound, the structural formula of which is shown in P5:

[0140]

[0141] The poly (1,2,4-thiadiazole) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (VI):

[0142]

[0143] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anergy. M5 is [1,1'-biphenyl]-4,4'-bis(carboximide) dihydrochloride, which can be purchased from the market, and in this example, it was purchased from Anergy. M7 is 1,4-phenylisocyanate. In this example, DBU, DIPEA, or triethylamine were all purchased from Anergy.

[0144] The preparation steps of the poly (1,2,4-thiadiazole) compound are as follows:

[0145] In a 10 mL polymerization tube (air atmosphere), monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 62.2 mg (0.2 mmol) of monomer M5 and 27.2 mg (0.2 mmol) of monomer M7 were sequentially added, 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, 1-10 of DIPEA was added, and the reaction was carried out at 70°C for 5h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO, then it was added dropwise into methanol, then it was left to stand, filtered, and dried at 20°C to obtain the poly(1,2,4-thiadiazole) compound P5.

[0146] According to the measured analysis, the yield of the poly(1,2,4-thiadiazole) compound P5 was 84%, the weight average molecular weight was 8500 g / mol, and the molecular weight distribution was 1.31. After P5 (30 mg) prepared in this example was dissolved in chlorobenzene, it was filtered through a 200 μm nylon filter membrane, and 40 μL of the filtrate was dropped on a 2 cm*2 cm silicon wafer for spin coating. The selected spin coater was a KW-41 type, the rotation speed was 1000 rpm, the prepared film was vacuum dried for 2h, and then the refractive index test was carried out by a variable angle spectroscopic ellipsometer, the wavelength range was 400-1700 nm, the film thickness was 128 nm, and the results showed that the refractive index of the polymer P5 film at 589 nm was 1.8654.

[0147] Example 6

[0148] A poly(amidino-thiourea) compound, the structural formula of which is shown as P1a:

[0149]

[0150] The poly(amidino-thiourea) compound is prepared by direct reaction of elemental sulfur, binary isocyanide, binary amide hydrochloride and base, and the reaction equation is shown as formula (VII):

[0151]

[0152] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it is purchased from Angene Company. M2 is 1,4-benzenedicarboxamide hydrochloride, which can be purchased from the market, and in this example, it is purchased from Angene Company. M3 is 1,4-benzyl isocyanide. In this example, DBU, DIPEA or triethylamine are all purchased from Angene Company.

[0153] The preparation steps of the poly(amidino-thiourea) compound are as follows:

[0154] In a 10-mL polymerization tube, monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 47.0 mg (0.2 mmol) of monomer M2 and 31.2 mg (0.2 mmol) of monomer M3 were sequentially added, vacuumed and replaced with nitrogen for 3 times, 1 mL of dimethyl sulfoxide (DMSO) was injected by a syringe, 1-10 of DIPEA was added, and the reaction was carried out at 45°C for 7 h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO, and then was added dropwise into methanol, followed by standing, filtration and drying at 20°C to obtain the poly(amidino-thiourea) compound P1a.

[0155] According to the measured analysis, the yield of the poly(amidino-thiourea) compound P1a was 82%, the weight average molecular weight was 9600 g / mol, and the molecular weight distribution was 1.29. After P1a (30 mg) prepared in this example was dissolved in chlorobenzene, it was filtered through a 200-μm nylon filter membrane, and 40 μL of the filtrate was dropped on a 2 cm*2 cm silicon wafer for spin coating. The selected spin coater was a KW-41 type, and the rotation speed was 1000 rpm. The prepared film was vacuum dried for 2 h, and then its refractive index was tested by a variable-angle spectroscopic ellipsometer at a wavelength range of 400-1700 nm. The film thickness was 108 nm, and the results showed that the refractive index of the polymer P1a film at 589 nm was 1.7126.

[0156] Figure 3 、 Figure 4 、 Figure 6 The structure of P1a was confirmed by nuclear magnetic resonance and infrared absorption spectrum, respectively. Figure 6 The infrared absorption spectrum of P1a is IR (KBr thin film), v (cm -1 ): 3229, 1693, 1568, 1520, 1447, 1404, 1334, 1287, 1090, 1015, 971, 857, 798, 711, 608, 471. Figure 3 and Figure 4 are the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of P1a, respectively. 1 H NMR (500 MHz, DMSO-d6), δ (TMS, ppm): 10.39 / 8.99 (s, 1H), 9.98 / 8.68 (s, 1H), 9.60 / 9.24 (t, 2H), 8.07-7.98 (m, 4H), 7.29-7.20 (m, 4H), 4.71 (d, J = 6.0 Hz, 2H), 4.59 (d, J = 6.0 Hz, 2H). 13CNMR (125 MHz, DMSO-d6), δ (TMS, ppm): 190.06 / 187.70 (C=S), 161.33 / 159.99 (C=N), 137.87 / 137.14, 127.58 / 127.52, 127.38 / 127.35, 127.19 / 127.14, 46.52 / 46.26.

[0157] Figure 8 The thermal gravimetric curve of the poly(amidino-thiourea) compound P1a shows that the polymer has good thermal stability sex . Figure 10 The refractive index graph of the film of the poly(amidino-thiourea) compound P1a shows that the refractive index of the polymer P1a film at 589 nm is 1.7126. It is much higher than the common polymer (1.5-1.6), and has potential application in the field of optics and optoelectronics.

[0158] Example 7

[0159] A poly(amidino-thiourea) compound, the structural formula of which is shown as P2a:

[0160]

[0161] The poly(amidino-thiourea) compound is prepared by direct reaction of elemental sulfur, binary isocyanide, binary amide hydrochloride and base, and the reaction equation is shown as formula (VIII):

[0162]

[0163] In the formula, monomer M1 is elemental sulfur, which can be purchased from the market, and in the present example, it is purchased from Angene Company. M2 is 1,4-benzenedicarboxamide hydrochloride, which can be purchased from the market, and in the present example, it is purchased from Angene Company. M4 is bis(4-isocyanide phenyl) methane. In the present example, DBU, DIPEA or triethylamine are all purchased from Angene Company.

[0164] The preparation steps of the poly(amidino-thiourea) compound are as follows:

[0165] In a 10 mL polymerization tube, monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 47.0 mg (0.2 mmol) of monomer M2 and 43.6 mg (0.2 mmol) of monomer M4 were sequentially added, then vacuumed and replaced with nitrogen for 3 times, 1 mL of dimethyl sulfoxide (DMSO) was injected by a syringe, then 1-10 DIPEA was added, and the reaction was carried out at 100°C for 3.5 h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO, then it was added dropwise into methanol, then it was left to stand, filtered and dried at 20°C to obtain the poly(amidino-thiourea) compound P2a.

[0166] After measurement and analysis, the yield of the poly(amidino-thiourea) compound P2a was 86%, the weight-average molecular weight was 26,500 g / mol, and the molecular weight distribution was 2.5. P2a (30 mg) prepared in this example was dissolved in chlorobenzene and then filtered through a 200 μm nylon filter membrane. 40 μL of the filtrate was dropwise applied to a 2 cm*2 cm silicon wafer and spin-coated. The selected spin-coating apparatus was a KW-41 model with a rotation speed of 1,000 rpm. The prepared film was vacuum-dried for 2 h and then subjected to a refractive index test using a variable angle spectroscopic ellipsometer over a wavelength range of 400-1,700 nm and a film thickness of 134 nm. The results showed that the refractive index of the polymer P2a film at 589 nm was 1.8069.

[0167] Example 8

[0168] A poly(amidino-thiourea) compound, the structural formula of which is shown in P3a:

[0169]

[0170] The poly (amidino-thiourea) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (IX):

[0171]

[0172] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anergy. M5 is [1,1'-biphenyl]-4,4'-bis(carboximide) dihydrochloride, which can be purchased from the market, in this example, purchased from Anergy. M3 is 1,4-phenylbenzyl isocyanide. In this example, DBU, DIPEA, or triethylamine were all purchased from Anergy.

[0173] The preparation steps of the poly (amidino-thiourea) compound are as follows:

[0174] In a 10 ml polymerization tube, monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 62.2 mg (0.2 mmol) of monomer M5 and 31.2 mg (0.2 mmol) of monomer M3 were added in sequence, and then vacuum was evacuated and replaced with nitrogen three times. 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10% of DIPEA was added. The reaction was carried out at 25°C for 0.5 h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20°C to obtain the poly (amidino-thiourea) compound P3a.

[0175] After measurement and analysis, the yield of the poly(amidino-thiourea) compound P3a was 75%, the weight-average molecular weight was 20,600 g / mol, and the molecular weight distribution was 1.78. P3a (30 mg) prepared in this example was dissolved in chlorobenzene and then filtered through a 200 μm nylon filter membrane. 40 μL of the filtrate was dropwise applied to a 2 cm*2 cm silicon wafer and spin-coated. The selected spin-coating apparatus was a KW-41 model with a rotation speed of 1000 rpm. The prepared film was vacuum-dried for 2 h and then subjected to a refractive index test using a variable angle spectroscopic ellipsometry over a wavelength range of 400-1700 nm and a film thickness of 128 nm. The results showed that the refractive index of the polymer P3a film at 589 nm was 1.7464.

[0176] Example 9

[0177] A poly(amidino-thiourea) compound, the structural formula of which is shown in P4a:

[0178]

[0179] The poly (amidino-thiourea) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (10):

[0180]

[0181] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anage. M2 is 1,4-benzenedicarboxylic acid amide hydrochloride, which can be purchased from the market, in this example, purchased from Anage. M6 is 1,4-diisocyanato-2,5-dimethylbenzene. In this example, DBU, DIPEA, or triethylamine were all purchased from Anage.

[0182] The preparation steps of the poly (amidino-thiourea) compound are as follows:

[0183] In a 10 ml polymerization tube, monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 47.0 mg (0.2 mmol) of monomer M2 and 31.2 mg (0.2 mmol) of monomer M6 were added in sequence, and then vacuum was evacuated and replaced with nitrogen three times. 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10% of DIPEA was added. The reaction was carried out at 40° C. for 8 h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20° C. to obtain the poly (amidino-thiourea) compound P4a.

[0184] After determination and analysis, the productive rate of poly (amidino-thiourea) compound P4a was 81%, the weight-average molecular weight was 22800g / mol, and the molecular weight distribution was 2.12. P4a (30mg) prepared in this embodiment was dissolved in chlorobenzene and then filtered through a 200μm nylon filter membrane. 40μL of the filtrate was dripped onto a 2cm*2cm silicon wafer and spin-coated. The selected spin coater model was KW-41, with a rotation speed of 1000rpm. The prepared film was vacuum-dried for 2h and then subjected to a refractive index test using a variable angle spectroscopic ellipsometry. The wavelength range was 400-1700nm, and the film thickness was 145nm. The result showed that the refractive index of the polymer P4a film at 589nm was 1.7842.

[0185] Example 10

[0186] A poly(amidino-thiourea) compound, the structural formula of which is shown in P5a:

[0187]

[0188] The poly(amidino-thiourea) compound is prepared by direct reaction of elemental sulfur, diisocyanate, diamide hydrochloride and base, and the reaction equation is as shown in Formula (11):

[0189]

[0190] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anergy. M5 is [1,1'-biphenyl]-4,4'-bis(carboximide) dihydrochloride, which can be purchased from the market, and in this example, it was purchased from Anergy. M7 is 1,4-phenylisocyanate. In this example, DBU, DIPEA, or triethylamine were all purchased from Anergy.

[0191] The preparation steps of the poly (amidino-thiourea) compound are as follows:

[0192] In a 10 ml polymerization tube, monomer M1 (0.8-4.0 mmol, 19.2-96.0 mg), 54.8 mg (0.2 mmol) of monomer M9 and 25.6 mg (0.2 mmol) of monomer M5 were added in sequence, and then vacuum was evacuated and replaced with nitrogen three times. 1 mL of dimethyl sulfoxide (DMSO) was injected with a syringe, and then 1-10% of DIPEA was added. The reaction was carried out at 60° C. for 0.5 h. After the reaction was completed, the reaction mother liquor was dissolved in 2 mL of DMSO and then added dropwise to methanol. The mixture was allowed to stand, filtered, and dried at 20° C. to obtain the poly (amidino-thiourea) compound P5a.

[0193] After determination and analysis, the productive rate of poly (amidino-thiourea) compound P5a was 77%, the weight average molecular weight was 16500g / mol, and the molecular weight distribution was 1.75. After the P5a (30mg) prepared in this embodiment was dissolved in chlorobenzene, it was then filtered through a 200μm nylon filter membrane, and 40μL of the filtrate was dripped onto a 2cm*2cm silicon wafer for spin coating. The selected spin coater model was KW-41 type, and the rotating speed was 1000rpm. The prepared film was vacuum dried for 2h and then subjected to a refractive index test using a variable angle spectroscopic ellipsometry. The wavelength range was 400-1700nm, and the film thickness was 145nm. The result showed that the refractive index of the polymer P5a film at 589nm was 1.8107.

[0194] Example 11

[0195]

[0196] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anage. M8 is benzamidine hydrochloride, which can be purchased from the market, in this example, purchased from Bitec. M9 is 2,6-dimethylphenyl isocyanide, which can be purchased from the market, in this example, purchased from Anage. In this example, DBU, DIPEA, or triethylamine were all purchased from Anage.

[0197] The preparation steps of the guanylthiourea small molecule are as follows:

[0198] To a 10 ml polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 131 mg (1 mmol) of monomer M9 were added sequentially. The mixture was then evacuated and replaced with nitrogen three times. 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12 mmol of DIPEA. The mixture was reacted at 100°C for 0.5 h. After completion, 50 mL of water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and the solvent was removed by rotary evaporation in vacuo to obtain a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 6 / 1) as eluent to obtain guanylthiourea compound M10. 1 H NMR (400MHz, DMSO-d6), δ (TMS, ppm): 10.54 / 10.28 (s, 1H), 10.07 / 8.86 (s, 2H), 8.06-8. 04(m,1H),7.60-7.44(m,3H),7.33-7.30(m,1H),7.10-7.08(m,3H),2.18 / 2.15(s,6H). 13C NMR(125MHz,DMSO-d6)δ190.14 / 188.35(C=S),162.33 / 161.64(C=N),137.96 / 136.79,135.99 / 135.34,135.05 / 134.95,1 31.74 / 131.57,128.33 / 128.26,127.68 / / 127.53,127.37 / 127.31,126.86 / 126.51,18.16,18.04.HRMS(ESI):m / z:calcd for[C 16 H 17 N3S+H + ]:284.1216; found 284.1220.

[0199] Example 12

[0200]

[0201] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anaiji. M8 is benzamidine hydrochloride, which can be purchased from the market, and in this example, it was purchased from Bidex. M11 is benzyl isocyanide, which can be purchased from the market, and in this example, it was purchased from Anaiji. In this example, DBU, DIPEA, or triethylamine were all purchased from Anaiji.

[0202] The preparation steps of the guanylthiourea small molecule are as follows:

[0203] To a 10 ml polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 117.2 mg (1 mmol) of monomer M11 were added sequentially. The mixture was then evacuated and replaced with nitrogen three times. 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12 mmol of DIPEA. The mixture was reacted at 80°C for 3.5 h. After completion, 50 mL of water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and the solvent removed by rotary evaporation in vacuo to obtain a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 7 / 1) as eluent to obtain guanylthiourea compound M12.

[0204] Example 13

[0205]

[0206] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anaiji. M8 is benzamidine hydrochloride, which can be purchased from the market, and in this example, it was purchased from Bidex. M13 is phenyl isocyanide, which can be purchased from the market, and in this example, it was purchased from Anaiji. In this example, DBU, DIPEA, or triethylamine were all purchased from Anaiji.

[0207] The preparation steps of the guanylthiourea small molecule are as follows:

[0208] To a 10 ml polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 103.1 mg (1 mmol) of monomer M13 were added sequentially. The mixture was then evacuated and replaced with nitrogen three times. 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12 mmol of DIPEA. The mixture was reacted at 100°C for 5 h. After completion, 50 mL of water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and the solvent removed by rotary evaporation in vacuo to obtain a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 7 / 1) as eluent to obtain guanylthiourea compound M14.

[0209] Example 14

[0210]

[0211] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anaiji. M8 is benzamidine hydrochloride, which can be purchased from the market, and in this example, it was purchased from Bidex. M15 is tert-butyl isocyanate, which can be purchased from the market, and in this example, it was purchased from Anaiji. In this example, DBU, DIPEA, or triethylamine were all purchased from Anaiji.

[0212] The preparation steps of the guanylthiourea small molecule are as follows:

[0213] To a 10 ml polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 83.1 mg (1 mmol) of monomer M15 were added sequentially. The mixture was then evacuated and replaced with nitrogen three times. 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12 mmol of DIPEA. The mixture was allowed to react at 120°C for 0.5 h. After completion, 50 mL of water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and the solvent removed by rotary evaporation in vacuo to yield a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 10 / 1) as eluent to yield guanylthiourea compound M16.

[0214] Example 15

[0215]

[0216] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, in this example, purchased from Anage. M8 is benzamidine hydrochloride, which can be purchased from the market, in this example, purchased from Bitec. M9 is 2,6-dimethylphenyl isocyanide, which can be purchased from the market, in this example, purchased from Anage. In this example, DBU, DIPEA, or triethylamine were all purchased from Anage.

[0217] The preparation steps of the 1,2,4-thiadiazole small molecule are as follows:

[0218] To a 10-mL polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 131 mg (1 mmol) of monomer M9 were added sequentially. 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12% DIPEA. The mixture was allowed to react at 120°C for 4 h. After completion, 50 mL of water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the organic phases were combined and the solvent removed by rotary evaporation in vacuo to yield a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 6 / 1) as eluent to yield 1,2,4-thiadiazole compound M17. 1 H NMR (400MHz, DMSO-d6), δ (TMS, ppm): 10.21 (s, 1H, -NH-), 8.20-8.07 (m, 2H), 7.48-7.44 (m, 3H), 7.19 (s, 3H), 2.24 (s, 6H). 13 C NMR(125MHz,DMSO-d6)δ184.03,169.20,136.95,135.55,133.07,129.96,128.78,128.64,127.78,127.48,17.75.HRMS(ESI):m / z:calcd for[C 16 H 15 N3S+H + ]:282.1073;found282.1059.

[0219] Example 17

[0220]

[0221] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anaiji. M8 is benzamidine hydrochloride, which can be purchased from the market, and in this example, it was purchased from Bidex. M11 is benzyl isocyanide, which can be purchased from the market, and in this example, it was purchased from Anaiji. In this example, DBU, DIPEA, or triethylamine were all purchased from Anaiji.

[0222] The preparation steps of the 1,2,4-thiadiazole small molecule are as follows:

[0223] To a 10 ml polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 117.2 mg (1 mmol) of monomer M11 were added sequentially. The mixture was then evacuated and replaced with nitrogen three times. 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12 mmol of DIPEA. The mixture was allowed to react at 25°C for 8 h. After completion, 50 mL of water was added to quench the reaction, followed by extraction three times with ethyl acetate. The organic phases were combined and the solvent removed by rotary evaporation in vacuo to yield the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 7 / 1) as eluent to yield the 1,2,4-thiadiazole compound M18.

[0224] Example 18

[0225]

[0226] Among them, monomer M1 is elemental sulfur, which can be purchased from the market, and in this example, it was purchased from Anaiji. M8 is benzamidine hydrochloride, which can be purchased from the market, and in this example, it was purchased from Bidex. M15 is tert-butyl isocyanate, which can be purchased from the market, and in this example, it was purchased from Anaiji. In this example, DBU, DIPEA, or triethylamine were all purchased from Anaiji.

[0227] The preparation steps of the 1,2,4-thiadiazole small molecule are as follows:

[0228] To a 10-mL polymerization tube, monomer M1 (1.5-4.0 mmol, 48-96.0 mg), 156.6 mg (1 mmol) of monomer M8, and 83.1 mg (1 mmol) of monomer M15 were added sequentially. Then, 4 mL of acetonitrile (MeCN) was injected via syringe, followed by 2.5-12% DIPEA. The mixture was allowed to react at 90°C for 8 h. After completion, 50 mL of water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the organic phases were combined and the solvent removed by rotary evaporation in vacuo to yield the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (v / v = 10 / 1) as eluent to yield 1,2,4-thiadiazole compound M19.

[0229] As can be seen from the above examples, the present invention provides a series of guanylthioureas and 1,2,4-thiadiazole small molecules, poly(1,2,4-thiadiazole) and poly(guanyl-thiourea) compounds, as well as preparation methods and applications thereof. The preparation methods of the present invention feature readily available raw materials, mild reaction conditions, simple processes, and high product yields. Experimental verification indicates that the poly(1,2,4-thiadiazole) and poly(guanyl-thiourea) compounds of the present invention have a high refractive index due to the introduction of sulfur atoms, and have potential applications in the fields of optics and optoelectronics.

[0230] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a sulfur-containing compound and a sulfur-containing polymer, characterized in that: The sulfur-containing polymer includes a poly(1,2,4-thiadiazole) compound and a poly(guanyl-thiourea) compound; the sulfur-containing compound includes a guanylthiourea and a 1,2,4-thiadiazole; (1) The preparation method of the poly (1,2,4-thiadiazole) compound comprises the following steps: In an oxidizing atmosphere, elemental sulfur, a polyisocyanide compound, a polyamide compound, and a base compound are added to an organic solvent to obtain a mixed solution, and the mixture is heated under stirring to perform a polymerization reaction to obtain a poly(1,2,4-thiadiazole) compound; (2) The preparation method of the poly(amidino-thiourea) compound comprises the following steps: Under a protective atmosphere, elemental sulfur, a polyisocyanide compound, a polyamide compound, and a base compound are added to an organic solvent to obtain a mixed solution, and the mixture is heated under stirring to perform a polymerization reaction to obtain a poly(amidino-thiourea) compound; (3) The preparation method of the 1,2,4-thiadiazole comprises the following steps: Under an oxidizing atmosphere, elemental sulfur, an isonitrile compound, an amide compound, and a base compound are added to an organic solvent to obtain a mixed solution, and the mixture is heated under stirring to react to obtain a sulfur-containing compound 1,2,4-thiadiazole; the isonitrile compound includes a monobasic isonitrile compound and a polybasic isonitrile compound, the amide compound includes a monobasic amide compound and a polybasic amide compound, and at least one of the isonitrile compound and the amide compound is a monobasic compound; (4) The preparation method of the guanyl-thiourea comprises the following steps: Under a protective atmosphere, elemental sulfur, an isocyanide compound, an amide compound and an alkaline compound are added to an organic solvent to obtain a mixed liquid, which is then heated under stirring to react to obtain a sulfur-containing compound guanyl-thiourea; the isocyanide compound includes a monobasic isocyanide compound and a polybasic isocyanide compound, the amide compound includes a monobasic amide compound and a polybasic amide compound, and at least one of the isocyanide compound and the amide compound is a monobasic compound.

2. The preparation method according to claim 1, characterized in that The structural formula of the poly (1,2,4-thiadiazole) compound is one of the following general structural formulas: The structural formula of the poly(amidino-thiourea) compound is one of the following general structural formulas: The general structural formulas of the guanyl-thiourea and 1,2,4-thiadiazole are respectively Wherein, n is an integer between 2 and 400; R 1 、R 2 、R 3 、R 4 are independently selected from organic groups.

3. The preparation method according to claim 2, characterized in that R 1 、R 2 、R 3 、R 4 are independently selected from aryl or alkyl.

4. The preparation method according to claim 1, characterized in that The polybasic isonitrile compound is a dibasic isonitrile compound, the polybasic amide compound is a dibasic amide compound; and the amide compound is amide hydrochloride.

5. The preparation method according to claim 4, characterized in that The diamide compound comprises the following structural formula: The binary isonitrile compound comprises the following structural formula: The monoamide compound comprises the following structural formula: The monobasic isonitrile compound comprises the following structural formula:

6. The preparation method according to claim 1, characterized in that The base compound in methods (1), (2), (3) and (4) comprises one or more of triethylamine, N,N-diisopropylethylamine, potassium carbonate, cesium carbonate, triethylenediamine and sodium carbonate; The organic solvent in methods (1), (2), (3) and (4) is one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, acetonitrile, 1,4-dioxane, tetrahydrofuran and 1,2-dichloromethane; The molar ratio of elemental sulfur, polyisocyanate compound, polyamide compound and base compound in methods (1) and (2) is 2-8:1:1:1.5-8; The molar ratio of elemental sulfur, isonitrile compound, amide compound and base compound in methods (3) and (4) is 2-8:1:1:1.5-8.

7. The preparation method according to claim 1, characterized in that The concentration of the polyamide compound in the mixed solution of methods (1) and (2) is 0.05 to 1 mol / L; the concentration of the amide compound in the mixed solution of methods (3) and (4) is 0.05 to 1 mol / L; The reaction temperature in methods (1), (2), (3) and (4) is 25 to 120° C., and the reaction time is 0.5 to 8 h. The oxidizing atmosphere in methods (1) and (3) is an air atmosphere; The protective atmosphere in methods (2) and (4) is an inert atmosphere.

8. The preparation method according to claim 1, characterized in that After the reaction in methods (1) and (2) is completed, the reaction mother liquor is dissolved in an organic solvent, and then added to a precipitant for precipitation, the precipitate is collected, and dried to a constant weight; the precipitant comprises one or more of methanol, n-hexane, and ethanol; the drying temperature is 20 to 30°C; After the reaction in methods (3) and (4) is completed, water is added to quench the reaction, and the mixture is extracted with ethyl acetate. The organic phases are combined and the solvent is removed by vacuum rotary evaporation to obtain a crude product, which is purified by silica gel column chromatography using petroleum ether / ethyl acetate as eluent.

9. The sulfur-containing compound and sulfur-containing polymer prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the sulfur-containing compound and sulfur-containing polymer according to claim 9 in the preparation of light-emitting electrochemical cells, optical waveguides, infrared reflective coatings, anti-reflective coatings, CMOS image sensors and infrared thermal imaging materials.

Images