A poly (O, O'-monothiocarbonate) compound and its preparation method and application

Abstract

The present invention provides a poly(O,O'-monothiocarbonate) compound and its preparation method and application, belonging to the technical field of sulfur-containing polymers. The present invention carries out a polymerization reaction of silyl ether, elemental sulfur and difluorocarbene reagent under the action of an organic base, dissolves the obtained polymer product in an organic solvent and adds a precipitant for precipitation, and the obtained precipitate is a poly(O,O'-monothiocarbonate) compound. The poly(O,O'-monothiocarbonate) compound prepared by the present invention has a clear chain structure, and the prepared film refractive index reaches 1.6188, with outstanding optical properties; and the reaction raw materials of the preparation method of the present invention are easily available and can be directly purchased commercially, with the advantages of low raw material price, mild synthesis conditions, simple process and high polymerization efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of sulfur-containing polymers, in particular to a poly(O,O'-monothiocarbonate) compound and a preparation method and application thereof. Background Art

[0002] Poly(O,O′-monothiocarbonate) is a typical sulfur-containing polymer with a structure similar to polycarbonate. However, due to the introduction of sulfur, it has unique properties such as excellent refractive index, high dielectric constant, crystallinity and chemical corrosion resistance, and has attracted increasing attention. Currently, methods for synthesizing aliphatic poly(O,O′-monothiocarbonates) include the ring-opening copolymerization of carbon disulfide with epoxides, carbon oxysulfide with epoxides, or oxygen- and sulfur-containing heterocyclic monomers. These methods suffer from limitations such as expensive raw materials, difficulty synthesizing monomer types, high reagent toxicity, and non-specific products, making it impossible to synthesize main-chain aromatic poly(O,O′-monothiocarbonates). Aromatic poly(O,O′-monothiocarbonates) are synthesized by copolymerizing bisphenol (alcohol) monomers with thiophosgene in the presence of a phase transfer catalyst and an alkaline solution. However, the raw material thiophosgene used in this method is highly toxic, difficult to store, and highly corrosive, hindering the development of new poly(O,O′-monothiocarbonates). This highlights the urgent need for novel, efficient, and universal synthetic methods to obtain a wider range of poly(O,O′-monothiocarbonate) structures with customized properties. Compared with the raw materials currently used to synthesize poly(O,O′-monothiocarbonate), such as oxygen or sulfur heterocycles, thiophosgene, etc., elemental sulfur has the advantages of huge raw material reserves, low price, easy storage, and non-corrosiveness. Directly using it as a sulfur source for the synthesis of poly(O,O′-monothiocarbonate) not only avoids the use of highly toxic thiophosgene, but also improves the utilization rate of elemental sulfur.

[0003] Therefore, developing a poly(O,O′-monothiocarbonate) synthesis method based on elemental sulfur with mild reaction conditions and strong universality has very important scientific and industrial value. Summary of the Invention

[0004] The present invention aims to provide a poly(O,O'-monothiocarbonate) compound and its preparation method and application, so as to solve the technical problems of high toxicity of raw materials and non-specific main chain structure of products caused by the current synthesis of poly(O,O'-monothiocarbonate).

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a poly(O,O′-monothiocarbonate) compound, comprising the following steps:

[0007] The silyl ether, elemental sulfur and difluorocarbene reagent are polymerized under the action of an organic base, the obtained polymer product is dissolved in an organic solvent and a precipitant is added to precipitate, and the obtained precipitate is a poly(O,O'-monothiocarbonate) compound.

[0008] Furthermore, the silyl ether is a divalent silyl ether or a polyvalent silyl ether.

[0009] Furthermore, the silyl ether is selected from any one of the following compounds:

[0010]

[0011] Here, k is an integer from 1 to 20.

[0012] Furthermore, when the silyl ether is a disilyl ether, the molar ratio of the disilyl ether, elemental sulfur, difluorocarbene reagent and organic base is 1:2-6:1-3:0.05-0.5;

[0013] When the silyl ether is a polysilyl ether, the molar ratio of the polysilyl ether, elemental sulfur, difluorocarbene reagent and organic base is 1:2-10:1-4:0.1-0.8.

[0014] Furthermore, the polymerization reaction is carried out in a protective gas atmosphere, and the protective gas comprises nitrogen and / or argon;

[0015] The polymerization reaction is carried out in an organic solvent, and the organic solvent comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dichloromethane and chloroform;

[0016] The concentration of the silyl ether in the reaction system is 0.2-2.00 mol / L.

[0017] Furthermore, the polymerization reaction temperature is 40-100° C., and the polymerization reaction time is 0.1-3 h.

[0018] Furthermore, the organic base is selected from one or more of the following compounds:

[0019]

[0020] Furthermore, the difluorocarbene reagent comprises Ph3P + CF2COO - , one of BrCF2COONa and ClCF2COONa; the precipitant is methanol.

[0021] The present invention also provides a poly(O,O'-monothiocarbonate) compound, wherein the poly(O,O'-monothiocarbonate) compound has one of the following general structural formulas:

[0022]

[0023] Wherein, n is an integer from 4 to 600, R 1 、R 2 R is independently an alkyl or aryl group, 3 is an aryl group, R 4 It is an aryl group.

[0024] The present invention also provides an application of a poly(O,O'-monothiocarbonate) compound in the preparation of a high refractive index film or an optical device.

[0025] Beneficial effects of the present invention:

[0026] (1) The reaction raw materials used in the preparation method of the present invention are readily available and the preparation is simple;

[0027] (2) The polymerization conditions of the present invention are mild, the process is simple, and the polymerization efficiency is high;

[0028] (3) The preparation method of the present invention has strong group tolerance and can introduce a variety of functional groups into the monomer;

[0029] (4) The compound poly(O,O′-monothiocarbonate) has good film-forming properties, thermal stability and refractive index. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Structural representations of monomer 1a, model compound M, and poly(O,O′-monothiocarbonate) P1;

[0031] Figure 2 For monomer 1a 1 H NMR spectrum;

[0032] Figure 3 For monomer 1a 13 C NMR spectrum;

[0033] Figure 4 For the model molecule M 1 H NMR spectrum;

[0034] Figure 5 For the model molecule M 13 C NMR spectrum;

[0035] Figure 6 For poly (O, O'-monothiocarbonate) P1 1 H NMR spectrum;

[0036] Figure 7 For poly (O, O'-monothiocarbonate) P1 13 C NMR spectrum;

[0037] Figure 8 Thermogravimetric curves of polymers P1 and P2;

[0038] Figure 9 Ellipsometry data of polymers P1 and P2;

[0039] Figure 10 The transmittance curves of polymers P1 and P2. DETAILED DESCRIPTION

[0040] The present invention provides a method for preparing a poly(O,O′-monothiocarbonate) compound, comprising the following steps:

[0041] The silyl ether, elemental sulfur and difluorocarbene reagent are polymerized under the action of an organic base, the obtained polymer product is dissolved in an organic solvent and a precipitant is added to precipitate, and the obtained precipitate is a poly(O,O'-monothiocarbonate) compound.

[0042] In the present invention, the elemental sulfur is sublimed sulfur.

[0043] In the present invention, the silyl ether is a disilyl ether or a polysilyl ether, preferably any one of the following compounds:

[0044]

[0045] Here, k is an integer of 1 to 20, and preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0046] In the present invention, when the silyl ether is disilyl ether, the molar ratio of disilyl ether, elemental sulfur, difluorocarbene reagent and organic base is 1:2-6:1-3:0.05-0.5, preferably 1:2.6-5.5:1.3-2.5:0.05-0.5, and more preferably 1:2.8:1.4:0.2.

[0047] In the present invention, when the silyl ether is a polysilyl ether, the molar ratio of the polysilyl ether, elemental sulfur, difluorocarbene reagent and organic base is 1:2-10:1-4:0.1-0.8, preferably 1:3-7:2.5-3.5:0.2-0.4.

[0048] In the present invention, the polymerization reaction is carried out in a protective gas atmosphere, the protective gas comprises nitrogen and / or argon, preferably nitrogen; the polymerization reaction is carried out in an organic solvent, the organic solvent comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dichloromethane and chloroform, preferably one or more of N,N-dimethylacetamide, tetrahydrofuran and dichloromethane, further preferably a mixed solution of N,N-dimethylacetamide and tetrahydrofuran, with a volume ratio of 3:2.

[0049] In the present invention, the concentration of the silyl ether in the reaction system is 0.2 to 2 mol / L, preferably 0.25 to 0.5 mol / L, and more preferably 0.25 mol / L.

[0050] In the present invention, the polymerization reaction temperature is 40-100° C., preferably 50-90° C., more preferably 60-80° C.; the polymerization reaction time is 0.1-3 h, preferably 0.5-2 h, more preferably 1-1.5 h.

[0051] In the present invention, the polymerization reaction is carried out under stirring at a stirring speed of 200 to 600 rpm, preferably 300 to 500 rpm, and more preferably 400 rpm.

[0052] In the present invention, the organic base is preferably one or more of the following compounds:

[0053]

[0054] In the present invention, the difluorocarbene reagent is preferably Ph3P + CF2COO - , one of BrCF2COONa and ClCF2COONa; the precipitant is preferably methanol.

[0055] In the present invention, the Ph3P + CF2COO - The structural formula is:

[0056]

[0057] The present invention also provides a poly(O,O'-monothiocarbonate) compound, wherein the poly(O,O'-monothiocarbonate) compound has one of the following general structural formulas:

[0058]

[0059] wherein n is an integer of 4 to 600, preferably an integer of 50 to 500, and more preferably an integer of 100 to 400; R 1 、R2 R is independently an alkyl or aryl group, 3 is an aryl group, R 4 is an aryl group;

[0060] In the present invention, the poly(O,O′-monothiocarbonate) compound is preferably the following compound:

[0061]

[0062] The present invention also provides an application of a poly(O,O'-monothiocarbonate) compound in the preparation of a high refractive index film or an optical device.

[0063] The technical solutions provided by the present invention are 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.

[0064] Example 1

[0065] A poly(O,O′-monothiocarbonate) compound, the structural formula of which is shown in P1:

[0066]

[0067] The poly(O,O′-monothiocarbonate) compound is prepared by direct reaction of difluoroacetic acid phosphonium inner salt, elemental sulfur and disilyl ether, and the reaction formula is as follows:

[0068]

[0069] Among them, monomer 1a is bisphenol A silyl ether, and the synthesis method is referred to Nature Chemistry 2017, 9, 1083-1088. Elemental sulfur 2 is sublimed sulfur, which can be purchased from the market, and in this embodiment, it was purchased from Aladdin Company; monomer 3 is difluoroacetic acid phosphonium inner salt, which can be purchased from the market, and in this embodiment, it was purchased from Shangfu Technology Company.

[0070] The synthesis steps of the poly(O,O′-monothiocarbonate) compound are as follows: monomer 1a (0.50 mmol, 228 mg), monomer 2 (1.40 mmol, 45 mg), and monomer 3 (0.70 mmol, 249 mg) are weighed in a molar ratio of 1.0:2.8:1.4 and added sequentially to a 10 mL Schlenk tube equipped with a magnet. Under N2 protection, 0.8 mL of anhydrous THF is injected, and the mixture is stirred at room temperature for 5 minutes. 1.2 mL of a solution of N,N-dimethylacetamide containing 0.1 mmol of an organic base MTBD is then injected again. The mixture is heated to 70°C and stirred at 300 rpm for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature and filtered through a glass dropper plugged with cotton and cotton into 100 mL of methanol for sedimentation. A large amount of white solid precipitates, which is allowed to stand, filtered, and dried to obtain the poly(O,O′-monothiocarbonate) P1. The yield of P1 is 90%, and the weight-average molecular weight M w =16900 g / mol, M w / M n =1.54.

[0071] The comparison of the H NMR spectra of the poly(O,O′-monothiocarbonate) P1 compound, its corresponding monomer 1a and the model molecule M (* represents the solvent peak) is shown in Figure 1 The methyl and tert-butyl proton peaks (δ 0.16 and 0.93) of monomer 1a connected to the silicon atom disappeared after the reaction ( Figure 1 A and C), in the 13C NMR spectrum of P1, the characteristic peak of the C=S carbon in the O,O′-monothiocarbonate group appears at δ194.11, which is very consistent with the peak of the model molecule M at δ194.43, and there is only one carbon at δ194.11 in the low-field region, indicating that the functional group of the poly(O,O′-monothiocarbonate) repeating unit is only C=S and has a precise structure.

[0072] The structural formula of the model molecule M is:

[0073]

[0074] The hydrogen and carbon spectra of the model molecule M are shown in Figure 4 and Figure 5 .

[0075] NMR data of synthesized monomer 1a: The original hydrogen spectrum and carbon spectrum of monomer 1a are shown in Figure 2 and Figure 3 . 1H NMR (400MHz, DMSO-d6) δ (TMS, ppm): 7.06 (d, J = 8.7Hz, 4H), 6.73 (d, J = 8.6Hz, 4H), 1.57 (s, 6H), 0.93 (s, 18H), 0.16 (s, 12H). 13 C NMR (100MHz, DMSO-d6) δ (TMS, ppm): 152.70, 143.28, 127.49, 119.02, 41.23, 30.70, 25.55, 17.89, -4.50.

[0076] Characterization data of P1: original NMR spectrum is shown in Figure 6 and Figure 7 ,IR(KBr disk),v(cm -1 ):2968,1776,1664,1595,1503,1407,1387,1364,1310,1273,1188,1160,1102,1079,1014,837,715,553 1 H NMR (500MHz, DMSO-d6) δ (TMS, ppm): 7.35 (d, J = 8.5Hz, 4H), 7.22 (d, J = 8.2Hz, 4H), 1.68 (s, 6H). 13 C NMR (125MHz, DMSO-d6) δ (TMS, ppm): 194.11, 151.05, 148.48, 127.91, 121.27, 42.21, 30.41.

[0077] Thermal analysis showed that Figure 8 As shown, the thermal decomposition temperature of P1 is T d (weight loss 5%) is 302°C, which has good thermal stability.

[0078] Example 2

[0079] A poly(O,O′-monothiocarbonate) compound, the structural formula of which is shown in P2:

[0080]

[0081] The poly(O,O′-monothiocarbonate) compound is prepared by direct reaction of difluoroacetic acid phosphonium inner salt, elemental sulfur and disilyl ether, and the reaction formula is as shown in Formula (2):

[0082]

[0083] The synthesis method of monomer 1b is based on the literature Nature Chemistry 2017, 9, 1083-1088. Elemental sulfur 2 is sublimed sulfur, which can be purchased from the market, and in this example, it was purchased from Aladdin. Monomer 3 is difluoroacetic acid phosphonium inner salt, which can be purchased from the market, and in this example, it was purchased from Shangfu Technology Co., Ltd.

[0084] The synthesis steps of the poly(O,O′-monothiocarbonate) are as follows: Monomer 1b (0.50 mmol, 214 mg), monomer 2 (1.40 mmol, 45 mg), and monomer 3 (0.70 mmol, 249 mg) are weighed in a molar ratio of 1.0:2.8:1.4 and added sequentially to a 10 mL Schlenk tube equipped with a magnet. Under nitrogen protection, 0.8 mL of anhydrous THF is injected, and the mixture is stirred at room temperature for 5 minutes. 1.2 mL of a solution of N,N-dimethylacetamide containing 0.1 mmol of the organic base MTBD is then injected, and the temperature is raised to 70°C. The temperature is maintained constant and stirred at 300 rpm for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature and filtered through a glass dropper and cotton plug into 100 mL of methanol for sedimentation. A large amount of white solid precipitates, which is allowed to stand, filtered, and dried to obtain the poly(O,O′-monothiocarbonate) P2. The yield of P2 is 87%, and the weight-average molecular weight M w =10500g / mol, M w / M n =1.30,

[0085] Characterization data of P2: Figure 8 As shown, thermal analysis shows that the thermal decomposition temperature of P2 is T d (weight loss 5%) is 283℃, showing good thermal stability, IR (KBr disk), v (cm -1 ):3035,1771,1660,1597,1435,1415,1247,1216,1179,1157,1102,1015,818,715,498. 1 H NMR (400MHz, DMSO-d6) δ (TMS, ppm): 7.36 (d, J = 8.3 Hz, 4H), 7.23 (d, J = 8.1 Hz, 4H), 4.01 (s, 2H). 13 C NMR (100MHz, DMSO-d6) δ (TMS, ppm): 194.33, 151.53, 139.69, 130.01, 129.95, 121.75, 40.20.

[0086] Example 3

[0087] A poly(O,O′-monothiocarbonate) compound, the structural formula of which is shown in P3:

[0088]

[0089] The poly(O,O′-monothiocarbonate) compound is prepared by direct reaction of triphenylphosphine difluoroacetic acid inner salt, elemental sulfur and disilyl ether, and the reaction formula is as shown in Formula (III):

[0090]

[0091] The synthesis method of monomer 1c is described in Nature Chemistry 2017, 9, 1083-1088. Elemental sulfur 2 is sublimed sulfur, which can be purchased commercially, and in this embodiment, it was purchased from Aladdin. Monomer 3 is difluoroacetic acid phosphonium inner salt, which can be purchased commercially, and in this embodiment, it was purchased from Shangfu Technology Co., Ltd.

[0092] The synthesis steps of the poly(O,O′-monothiocarbonate) are as follows: monomer 1c (0.50 mmol, 221 mg), monomer 2 (1.40 mmol, 45 mg), and monomer 3 (0.70 mmol, 249 mg) are weighed in a molar ratio of 1.0:2.8:1.4 and added sequentially to a 10 mL Schlenk tube with a magnetic rod. Under N2 protection, 0.8 mL of anhydrous THF is injected and stirred at room temperature for 5 minutes. 1.2 mL of N,N-dimethylacetamide solution containing 0.1 mmol of organic base MTBD is injected again, the temperature is raised to 70°C, and the temperature is maintained constant and stirred at a rate of 300 rpm for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, and the reaction solution is filtered through a glass dropper plugged with cotton and cotton into 100 mL of methanol for sedimentation. A large amount of white solid is precipitated, and the mixture is allowed to stand, filtered, and dried to obtain the poly(O,O′-monothiocarbonate) P3 as a white solid with a yield of 80% and a weight-average molecular weight of M. w =13100 g / mol, M w / M n =1.35.

[0093] Characterization data of P3: IR (KBr disk), v (cm -1 ):3035.90,2967.11,2931.15,2874.20,1773.98,1658.01,1598.01,1502.92,1454.82,1415.48,1375.08,1274.20,1208.73,1181.31,1114.14,1045.20,1014.29,934.78,836.06,715.01,545.50. 1H NMR (400MHz, DMSO-d6) δ (TMS, ppm): 7.39 (d, J = 8.4Hz, 4H), 7.22 (d, J = 8.2Hz, 4H), 4.26 (q, J = 7.2Hz, 1H), 1.59 (d, J = 7.1Hz, 3H). 13 CNMR (100MHz, DMSO-d6), δ (TMS, ppm): 195.25 (C=S), 152.40, 145.60, 129.65, 122.65, 43.97, 22.51.

[0094] Example 4

[0095] A poly(O,O′-monothiocarbonate) compound, the structural formula of which is shown in P4:

[0096]

[0097] The poly(O,O′-monothiocarbonate) compound is prepared by direct reaction of triphenylphosphine difluoroacetic acid inner salt, elemental sulfur and disilyl ether, and the reaction formula is as shown in Formula (IV):

[0098]

[0099] The synthesis method of monomer 1d is described in Nature Chemistry 2017, 9, 1083-1088. Elemental sulfur 2 is sublimed sulfur, which can be purchased commercially, and in this embodiment, it was purchased from Aladdin. Monomer 3 is difluoroacetic acid phosphonium inner salt, which can be purchased commercially, and in this embodiment, it was purchased from Shangfu Technology Co., Ltd.

[0100] The synthesis steps of the poly(O,O′-monothiocarbonate) are as follows: monomer 1d (0.50 mmol, 235 mg), monomer 2 (1.40 mmol, 45 mg), and monomer 3 (0.70 mmol, 249 mg) are weighed in a molar ratio of 1.0:2.8:1.4 and added sequentially to a 10 mL Schlenk tube with a magnetic rod. Under N2 protection, 0.8 mL of anhydrous THF is injected and stirred at room temperature for 5 minutes. 1.2 mL of N,N-dimethylacetamide solution containing 0.1 mmol of organic base MTBD is injected again, the temperature is raised to 70°C, and the temperature is maintained constant and stirred at 300 rpm for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, and the reaction solution is filtered through a glass dropper plugged with cotton and cotton into 100 mL of methanol for sedimentation. A large amount of white solid is precipitated, and the mixture is allowed to stand, filtered, and dried to obtain the poly(O,O′-monothiocarbonate) P4 as a white solid with a yield of 87% and a weight-average molecular weight of M. w =11200 g / mol, M w / Mn =1.35.

[0101] Characterization data of P4: IR (KBr disk), v (cm -1 ):3039,2970,2936,2878,1895,1775,1660,1597,1503,1463,1407,1380,1311,1273,1189,1109,1080,1041,1014,937,883,834,551. 1 HNMR (400MHz, DMSO-d6) δ (TMS, ppm): 7.29 (t, J = 7.8Hz, 4H), 7.22 (d, J = 8.0Hz, 4H), 2.14 (d, J = 8.0Hz, 2H), 1.59 (s, 3H), 0.68 (t, J = 7.0Hz, 3H). 13 C NMR (100MHz, DMSO-d6) δ (TMS, ppm): 194.02 (C=S), 150.97, 147.47, 128.43, 121.19, 45.71, 33.46, 26.41, 9.11.

[0102] Application Examples

[0103] In Example 1, polymer P1 was prepared into a film and tested. 40 mg of polymer P1 was weighed and dissolved in 1 mL of N,N-dimethylacetamide. The film was then filtered through a 200 μm nylon filter membrane. 60 μL of the filtrate was dropped onto a 2.0 cm × 2.0 cm silicon wafer for spin coating. The selected spin coater model was KW-41, with a rotation speed of 2000 rpm and a spin coating time of 30 s. The prepared film was placed on a 100°C heating table and dried for 15 s. The refractive index of the film was then tested using a variable angle spectroscopic polarimeter. The selected instrument model was V-VASE. The wavelength range is 400 to 1700 nm, the film thickness is 189 nm, and its refractive index-wavelength spectrum is shown in the figure. Figure 9 As shown in the results, the refractive index of the polymer P1 film at a wavelength of 633 nm is 1.6188, the refractive index at 593 nm is 1.6211, and the Abbe number v D Reached 31,400-800nm ​​transmittance curve spectrum ( Figure 10 ) show that the transmittance of the P1 film at wavelengths above 400 nm is greater than 91%. The above data indicate that polythiourea P1 has excellent optical properties.

[0104] The refractive index of the film prepared from polymer P2 in Example 2 is 1.6439 at a wavelength of 633 nm and 1.6496 at a wavelength of 593 nm, and the Abbe number v DThe transmittance in the range of 400-800nm ​​is higher than 85%.

[0105] The above embodiments and application examples show that the present invention provides a poly(O,O′-monothiocarbonate) compound, a preparation method and application thereof. The poly(O,O′-monothiocarbonate) compound prepared by the present invention has a clear chain structure, and the prepared film has a refractive index of 1.6188, with outstanding optical properties. In addition, the reaction raw materials of the preparation method of the present invention are easily available and can be directly purchased commercially, and have the advantages of low raw material prices, mild synthesis conditions, simple process, and high polymerization efficiency.

[0106] 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 poly ( O,O' -monothiocarbonate) compound, characterized in that, The following steps are involved: The silyl ether, elemental sulfur and difluorocarbene reagent are polymerized under the action of an organic base, the obtained polymer product is dissolved in an organic solvent and a precipitant is added to precipitate, and the obtained precipitate is poly( O,O' -monothiocarbonate) compounds; The silyl ether is selected from any one of the following compounds: Wherein, k is an integer from 1 to 20; When the silyl ether is a disilyl ether, the molar ratio of the disilyl ether, elemental sulfur, difluorocarbene reagent and organic base is 1:2-6:1-3:0.05-0.5; When the silyl ether is a polysilyl ether, the molar ratio of the polysilyl ether, elemental sulfur, difluorocarbene reagent and organic base is 1:2-10:1-4:0.1-0.8; The polymerization reaction is carried out in an organic solvent, and the organic solvent comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dichloromethane and chloroform; The concentration of the silyl ether in the reaction system is 0.2-2 mol / L.

2. The poly( O,O' -monothiocarbonate) compound, characterized in that, The polymerization reaction is carried out in a protective gas atmosphere, wherein the protective gas comprises nitrogen and / or argon.

3. The poly( O,O' -monothiocarbonate) compound, characterized in that, The polymerization reaction temperature is 40-100° C., and the polymerization reaction time is 0.1-3 h.

4. The poly( O,O' -monothiocarbonate) compound, characterized in that, The organic base is selected from one or more of the following compounds: .

5. The poly ( O,O' -monothiocarbonate) compound, characterized in that, The difluorocarbene reagent contains Ph3P + CF2COO - , one of BrCF2COONa and ClCF2COONa; the precipitant is methanol.

6. The poly( O,O' -monothiocarbonate) compound preparation method prepared poly ( O,O' -monothiocarbonate) compound, characterized in that, The poly ( O,O' -monothiocarbonate) compounds have one of the following general structural formulas: ; Where n is an integer from 4 to 600, R 1 、R 2 R is independently an alkyl or aryl group, 3 is an aryl group, R 4 It is an aryl group.

7. Use of the poly(O,O'-monothiocarbonate) compound according to claim 6 in the preparation of high refractive index films or optical devices.

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