A polythiazole compound, a preparation method and application thereof

Abstract

The application discloses a polythiazole compound and a preparation method and application thereof; a structural formula of the polythiazole compound is as shown in formula I, formula II and formula III. The preparation method comprises the following steps: reacting a polybasic alkenone compound, a polybasic isonitrile compound and elemental sulfur under the catalysis of an alkali to obtain the polythiazole compound. The preparation method is mild in conditions, efficient in reaction, high in yield, novel in product structure, can avoid the use of dangerous reagents, and can realize in-situ construction of the polythiazole compound; and the polythiazole compound has high molecular weight, photoluminescence and high refractive performance.

Description

Technical Field

[0001] This invention relates to the field of organic chemistry, specifically to a polythiazole compound, its preparation method, and its applications. Background Technology

[0002] Sulfur-containing heterocyclic polymers hold an important position in nature not only due to their unique structures but also play a crucial role in organic optoelectronics, solar cells, and refractive materials, demonstrating enormous application potential. However, their structures and types are currently severely limited by a finite number of synthetic methods. Therefore, there is an urgent need to develop a series of simple, mild, and novel synthetic methods for sulfur-containing heterocyclic polymers, yielding products with novel structures. Elemental sulfur, as a member of the oxalate group, possesses advantages such as strong nucleophilicity, high molar refractive index, strong coordination ability, and multiple valence states. Introducing sulfur into polymers often brings unexpected functionalities to polymer materials. Studies have shown that sulfur-containing polymers constructed with sulfur atoms exhibit high refractive index, strong metal ion adsorption capacity, dielectric properties, and self-healing properties, showing broad application prospects in optoelectronic materials, industrial chemistry, and biomedical materials. Therefore, how to introduce sulfur atoms into polymers in a simple and environmentally friendly manner is gradually attracting increasing attention.

[0003] Sulfur, as a byproduct of the chemical industry, is abundant, inexpensive, and readily available, and is commonly used in the preparation of polythioamides and polythioureas. It is also used in the vulcanization and desulfurization of S8. Multicomponent polymerization has proven to be a powerful tool for preparing sulfur-containing polymers, offering advantages such as high reaction efficiency, mild reaction conditions, simple operation, high atom economy, and diverse structures.

[0004] Therefore, how to achieve both reactivity and stereoselectivity of the reaction has become a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a polythiazole compound, its preparation method and application.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] A polythiazole compound with the following structural formula:

[0008]

[0009]

[0010] Among them, R 1 Each is an aryl or aryl derivative; R1 2 R1 3Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group, R2 2 R2 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group, R3 2 R3 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group, R4 2 R4 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group; R 4 Independently, it is an aryl group or an aryl derivative; R 5 Independently, it is an alkyl, benzyl, aryl, or aryl derivative; R 6 R 7 Each is an aryl or aryl derivative; n is an integer from 2 to 4000, and the wavy line indicates a repeating polymer unit.

[0011] Preferred, R 1 Each is an independent substituted or unsubstituted phenyl group;

[0012] R 4 Independently, it can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted diphenyl ether group, a substituted or unsubstituted diphenyl sulfide group, a substituted or unsubstituted benzophenone group, a substituted or unsubstituted diphenylmethane group, a substituted or unsubstituted triphenylamino group, or a substituted or unsubstituted tetraphenylvinyl group;

[0013] R 5 Alkyl groups with 1-10 carbon atoms, substituted or unsubstituted phenyl groups, substituted or unsubstituted diphenyl ether groups, substituted or unsubstituted diphenyl sulfide groups, substituted or unsubstituted benzophenone groups, substituted or unsubstituted diphenylmethane groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted benzyl groups, substituted or unsubstituted triphenylamino groups, substituted or unsubstituted tetraphenylvinyl groups;

[0014] R 6 R 7 Each of the following is independently substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted benzophenone, substituted or unsubstituted diphenylmethane, substituted or unsubstituted triphenylamine, or substituted or unsubstituted tetraphenylvinyl.

[0015] The substituents in substituted phenyl, substituted diphenyl ether, substituted diphenyl sulfide, substituted benzophenone, substituted diphenylmethane, substituted biphenyl, substituted benzyl, substituted triphenylamino, and substituted tetraphenylvinyl are alkyl, alkoxy, hydroxyl, carboxyl, halogen, amino, phenyl, triphenylamino, and tetraphenylvinyl, respectively, with substituents being ... or tetraphenylvinyl, respectively, with substituents being alkyl, alkoxy, hydroxyl, carboxyl, halogen, or tetraphenylvinyl, respectively

[0016] The preparation method of the above-mentioned polythiazole compounds includes the following steps:

[0017] The polythiazole compounds are obtained by reacting polyene ketone compounds, polyisocyanates and elemental sulfur under the catalysis of an alkali.

[0018] The structural formula of the polyene ketone compound is:

[0019]

[0020]

[0021] The structural formula of the polyisocyanate compound is as follows:

[0022]

[0023] Preferably, the structural formula of the polyene ketone compound is as follows:

[0024]

[0025] R is an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, a phenyl group, a triphenylamine group, or a tetraphenylvinyl group.

[0026] Preferably, the structural formula of the polyene ketone compound is as follows:

[0027]

[0028] The alkyl chain can be a straight-chain alkyl or a branched alkyl.

[0029] Preferably, the structural formula of the polyisocyanate compound is as follows:

[0030]

[0031] Preferably, the base is one or more of organic and inorganic bases;

[0032] More preferably, the organic and inorganic bases include one or more of potassium fluoride, potassium carbonate, cesium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, sodium hydride, triethylenediamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, bis(triphenylphosphine)ammonium chloride, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, and triethylamine.

[0033] Preferably, the molar ratio of the polyene ketone compound, polyisocyanate compound, elemental sulfur, and base is 1–20:1–20:1–20:1–15.

[0034] Preferably, the reaction temperature is 25–120°C, and the reaction time is 0–36 h, and not 0.

[0035] Preferably, the reaction is carried out under a protective gas or in air;

[0036] More preferably, the protective gas is one of nitrogen and a rare gas (inert gas).

[0037] Preferably, the reaction is carried out in an organic solvent;

[0038] More preferably, the organic solvent is one or more selected from toluene, tetrahydrofuran, dimethyl sulfoxide, hydrocarbon organic solvents, alcohol organic solvents, ester organic solvents, and amide organic solvents;

[0039] More preferably, the concentration of the polyene ketone compound in the organic solvent is 0.01–6.0 mol / L; the concentration of the polyisocyanate compound in the organic solvent is 0.01–6.0 mol / L.

[0040] Preferably, after the reaction is completed, the reaction solution is diluted, filtered to obtain filtrate, and then dropped into a settling agent for sedimentation. The precipitate is collected and dried to constant weight.

[0041] More preferably, the reaction solution is diluted with 1 to 4 times the volume of dimethyl sulfoxide or tetrahydrofuran.

[0042] More preferably, the precipitant is an alcohol or a mixture thereof in any proportion with an aqueous solution;

[0043] More preferably, the precipitant is a mixed solution of methanol and water in a volume ratio of 6:1.

[0044] The above-mentioned polythiazole compounds are used in the preparation of polymer optoelectronic devices and as refractive materials.

[0045] This invention can obtain polythiazole compounds by using different catalysts and different gas atmospheres.

[0046] The polythiazole compounds of this invention possess certain optical properties, especially photoluminescence properties. Fluorescence emission spectroscopy tests show that they have certain fluorescence emission properties and are expected to be applied to the fabrication of polymer optoelectronic devices.

[0047] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0048] (1) The preparation method of the present invention uses elemental sulfur as a sulfur source and carries out a one-pot reaction without transition metal catalysis to achieve in-situ construction of sulfur-containing heterocyclic functional polymers; the conditions are mild, the reaction is efficient, the yield is high, the product structure is novel, and the use of dangerous reagents can be avoided, thus enabling the in-situ construction of polythiazole compounds.

[0049] (2) The preparation method of the present invention can obtain high yield and high molecular weight polythiazole compounds, does not require metal catalysts and greatly reduces the reaction temperature, and the post-processing and purification of the product are more thorough and the process is simple.

[0050] (3) The preparation method of the present invention can extend the substrates of polythiazole compounds to aromatic isonitriles and benzyl isonitrile monomers, thereby preparing a variety of polythiazole compounds with aromatic ring structures and benzyl structures. At the same time, the substrate functional groups have high tolerance and can be connected to the aromatic ring to obtain polymer materials with diverse functions.

[0051] (4) The polythiazole compounds of the present invention have high molecular weight, photoluminescence properties and high refractive properties. Attached Figure Description

[0052] Figure 1 Comparison of the 1H NMR spectra of the thiazole compounds, polythiazoles, enones, and isonitriles in deuterated dimethyl sulfoxide (DMSO) of Example 1; wherein, A is the 1H NMR spectrum of an enone in DMSO, B is the 1H NMR spectrum of a diisocyanate in DMSO, C is the 1H NMR spectrum of a small molecule model of a thiazole compound in DMSO, and D is the 1H NMR spectrum of the polythiazole compound prepared in Example 1 in DMSO.

[0053] Figure 2 Comparison of the 1H NMR spectra of the thiazole compounds, polythiazoles, enones, and isonitriles in deuterated dimethyl sulfoxide (DMSO) of Example 1; wherein, A is the 1C NMR spectrum of enones in DMSO, B is the 1C NMR spectrum of diisocyanates in DMSO, C is the 1C NMR spectrum of the thiazole compound model in DMSO, and D is the 1C NMR spectrum of the polythiazole compounds prepared in Example 1 in DMSO.

[0054] Figure 3The image shows a comparison of the infrared absorption spectra of small thiazole compounds, polythiazoles, enones, and isonitriles in deuterated dimethyl sulfoxide (DMSO) of Example 1. Specifically, A represents the infrared absorption spectrum of an enone in DMSO, B represents the infrared absorption spectrum of a diisocyanate in DMSO, C represents the infrared absorption spectrum of a small thiazole compound model in DMSO, and D represents the infrared absorption spectrum of the polythiazole compound obtained in Example 1 in DMSO.

[0055] Figure 4 The thermogravimetric curve of the polythiazole compound P1 prepared in Example 1 under a nitrogen atmosphere is shown, where the temperature at which the weight loss is 5% is 271°C.

[0056] Figure 5 The hydrogen nuclear magnetic resonance spectrum of the polythiazole compound P2 prepared in Example 2 in deuterated dimethyl sulfoxide.

[0057] Figure 6 The image shows the carbon NMR spectrum of the polythiazole compound P2 prepared in Example 2 in deuterated dimethyl sulfoxide.

[0058] Figure 7 The image shows the 1H NMR spectrum of the polythiazole compound P3 prepared in Example 3 in deuterated dimethyl sulfoxide.

[0059] Figure 8 The image shows the carbon NMR spectrum of the polythiazole compound P3 prepared in Example 3 in deuterated dimethyl sulfoxide.

[0060] Figure 9 The GPC curves are for the polythiazole compounds P1-P9 prepared in Examples 1-9.

[0061] Figure 10 The refractive index diagrams are for the polythiazole compounds P1-P9 prepared in Examples 1-9.

[0062] Figure 11 The fluorescence emission spectrum of the polythiazole compound P10 prepared in Example 10 is shown. Detailed Implementation

[0063] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0064] In the examples, the alkyl chains in the structural formulas are all straight-chain alkyl groups.

[0065] Example 1

[0066] A polythiazole compound, the structural formula of which is shown in P1:

[0067]

[0068] It is prepared by the following reaction:

[0069]

[0070] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M2 is diphenylisocyanate, synthesized according to literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased from the market, and in this example it was purchased from Anaiji.

[0071] The preparation steps of the polythiazole compound P1 are as follows:

[0072] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 38 mg (0.3 mmol) of 1,4-diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was complete, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain chiral polypropylamine compound P1 with a yield of 99%, a weight-average molecular weight of 16,400 g / mol, and a molecular weight distribution of 1.91.

[0073] The 1H NMR spectra of polythiazole compound P1 and thiazole compound molecule 4 are as follows: Figure 1 Carbon spectrum, such as Figure 2 Infrared absorption spectrum such as Figure 3 .

[0074] Infrared spectral data (KBr disk), ν (cm⁻¹): 2953, 2928, 2856, 1632, 1602, 1564, 1506, 1493, 1412, 1321, 1240, 1222, 1172, 1107, 1062, 1012, 931, 877, 833, 748, 600, 626.

[0075] 1H NMR spectrum (400MHz, DMSO-d6) δ (TMS, ppm): 7.41–6.55 (m, 16H), 6.44–5.93 (m, 4H), 2.43–2.36 (m, 4H), 1.47–1.44 (m, 4H), 1.20–1.15 (m, 8H), 0.89–0.78 (m, 6H).

[0076] Carbon NMR spectrum (100MHz, DMSO-d6) δ (TMS, ppm): 189.19, 186.10, 156.49, 147.76, 147.36, 138.01, 134.23, 132.72, 132.46, 130.21, 129.48, 128.96, 127.64, 123.98, 123.53, 117.16, 34.98, 30.60, 30.30, 21.92, 13.87.

[0077] The thermogravimetric curve of polythiazole compound P1 is as follows: Figure 4 The thermal decomposition temperature with a 5% weight loss is 271℃.

[0078] Among them, the structure of the thiazole compound 4 is shown in Figure 4.

[0079]

[0080] It is prepared by the following reaction:

[0081]

[0082] Wherein, 1 is elemental sulfur, which can be purchased from the market; in this example, it was purchased from Anaiji. 2 is an enone, which can be purchased from the market; in this example, it was purchased from Anaiji. 3 is 2,6-dimethylbenzeneisocyanate, which can be purchased from the market; in this example, it was purchased from Anaiji. DBU is 1,8-Diazabicyclo[5.4.0]undec-7-ene, which can be purchased from the market; in this example, it was purchased from Anaiji.

[0083] The preparation steps of the thiazole compound small molecule 4 are as follows:

[0084] In a clean 10 mL Schlenk polymerization tube, 64 mg (2.0 mmol) of elemental sulfur, 104 mg (0.50 mmol) of enone, and 79 mg (0.6 mmol) of 2,6-dimethylbenzeneisocyanate were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.038 mL (0.25 mmol) of DBU and 0.2 mL of dimethyl sulfoxide (DMSO) were added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After cooling to room temperature, 25 mL of dichloromethane was added, and the mixture was extracted three times. The extract was then vacuum rotary evaporated and separated by silica gel column chromatography to obtain thiazole compound 4 in 88% yield.

[0085] Example 2

[0086] A polythiazole compound, the structural formula of which is shown on P2:

[0087]

[0088] It is prepared by the following reaction:

[0089]

[0090] In this example, M3 is 4,4'-dimethyldienone, synthesized according to literature; M2 is 1,4-diisocyanate benzene, synthesized according to literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased from the market, and in this example it was purchased from Anaiji.

[0091] The preparation steps of the polythiazole compound P2 are as follows:

[0092] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 134 mg (0.30 mmol) of 4,4'-dimethyldienone, 38 mg (0.30 mmol) of 1,4-diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was complete, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton swabs to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain the polythiazole compound P2 (NMR spectrum as shown in Figure 1). Figure 5 Carbon spectrum, such as Figure 6 The yield was 87%, the weight-average molecular weight was 94,700 g / mol, and the molecular weight distribution was 3.96.

[0093] Example 3

[0094] A polythiazole compound, the structural formula of which is shown on page 3:

[0095]

[0096] It is prepared by the following reaction:

[0097]

[0098] In this example, M4 is a diene, synthesized according to literature; M2 is 1,4-diisocyanate benzene, synthesized according to literature; 1 is elemental sulfur, which can be purchased commercially, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased commercially, and in this example it was purchased from Anaiji.

[0099] The preparation steps of the polythiazole compound P3 are as follows:

[0100] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 101 mg (0.30 mmol) of 4,4'-dimethyldienone, 38 mg (0.3 mmol) of 1,4-diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain the polythiazole compound P3 (NMR spectrum as shown in Figure 1). Figure 7 Carbon spectrum, such as Figure 8 The yield was 86%, the weight-average molecular weight was 8,600 g / mol, and the molecular weight distribution was 1.36.

[0101] Example 4

[0102] A polythiazole compound, the structural formula of which is shown on page 4:

[0103]

[0104] It is prepared by the following reaction:

[0105]

[0106] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M5 is methylenebis(p-phenylene)]diisocyanate, synthesized according to literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased from the market, and in this example it was purchased from Anaiji.

[0107] The preparation steps of the polythiazole compound P4 are as follows:

[0108] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 65 mg (0.3 mmol) of methylenebis(p-phenylene)diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain polythiazole compound P4 with a yield of 95%, a weight-average molecular weight of 31,000 g / mol, and a molecular weight distribution of 1.78.

[0109] Example 5

[0110] A polythiazole compound, the structural formula of which is shown on page 5:

[0111]

[0112] It is prepared by the following reaction:

[0113]

[0114] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M6 is oxybis(p-phenylene)]diisocyanate, synthesized according to literature; 1 is elemental sulfur, which can be purchased commercially, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased commercially, and in this example it was purchased from Anaiji.

[0115] The preparation steps of the polythiazole compound P5 are as follows:

[0116] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 66 mg (0.3 mmol) of oxybis(p-phenylene)diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain polythiazole compound P5 with a yield of 98%, a weight-average molecular weight of 63,900 g / mol, and a molecular weight distribution of 2.71.

[0117] Example 6

[0118] A polythiazole compound, the structural formula of which is shown on page 6:

[0119]

[0120] It is prepared by the following reaction:

[0121]

[0122] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M6 is thiobis(p-phenylene)]diisocyanate, synthesized according to literature; 1 is elemental sulfur, which can be purchased commercially, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased commercially, and in this example it was purchased from Anaiji.

[0123] The preparation steps of the polythiazole compound P6 are as follows:

[0124] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 67 mg (0.3 mmol) of oxybis(p-phenylene)diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain polythiazole compound P6 with a yield of 90%, a weight-average molecular weight of 18,600 g / mol, and a molecular weight distribution of 2.20.

[0125] Example 7

[0126] A polythiazole compound, the structural formula of which is shown on page 7:

[0127]

[0128] It is prepared by the following reaction:

[0129]

[0130] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M7 is bis(biphenyl)]diisocyanate, synthesized according to literature; 1 is elemental sulfur, which can be purchased commercially, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased commercially, and in this example it was purchased from Anaiji.

[0131] The preparation steps of the polythiazole compound P7 are as follows:

[0132] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 61 mg (0.3 mmol) of bis(biphenyl)diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction was performed three times under vacuum and nitrogen purging. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain polythiazole compound P7 with a yield of 97%, a weight-average molecular weight of 30,800 g / mol, and a molecular weight distribution of 1.92.

[0133] Example 8

[0134] A polythiazole compound, the structural formula of which is shown on page 8:

[0135]

[0136] It is prepared by the following reaction:

[0137]

[0138] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M8 is diisocyanate, synthesized according to literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased from the market, and in this example it was purchased from Anaiji.

[0139] The preparation steps of the polythiazole compound P8 are as follows:

[0140] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 91 mg (0.3 mmol) of diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction mixture was evacuated and purged with nitrogen three times. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain polythiazole compound P8 with a yield of 65%, a weight-average molecular weight of 15,000 g / mol, and a molecular weight distribution of 1.92.

[0141] Example 9

[0142] A polythiazole compound, the structural formula of which is shown on page 9:

[0143]

[0144] It is prepared by the following reaction:

[0145]

[0146] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature; M9 is dibenzyl isonitrile, synthesized according to literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anaiji; DABCO is triethylenediamine, which can be purchased from the market, and in this example it was purchased from Anaiji.

[0147] The preparation steps of the polythiazole compound P9 are as follows:

[0148] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 171 mg (0.3 mmol) of ketene, 47 mg (0.3 mmol) of dibenzyl isonitrile, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction mixture was evacuated and purged with nitrogen three times. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain polythiazole compound P9 with a yield of 65%, a weight-average molecular weight of 8200 g / mol, and a molecular weight distribution of 1.31.

[0149] Example 10

[0150] A polythiazole compound, the structure of which is shown on P10.

[0151]

[0152] It is prepared by the following reaction:

[0153]

[0154] Wherein, 1 is elemental sulfur, which is commercially available; in this example, it was purchased from Anaiji. M10 is tetraphenylethylene-substituted diene, synthesized according to literature. M2 is 1,4-diisocyanate benzene, synthesized according to literature. DBU is 1,8-Diazabicyclo[5.4.0]undec-7-ene. DABCO is triethylenediamine, which is commercially available; in this example, it was purchased from Anaiji.

[0155] The preparation steps of the polythiazole compound P10 are as follows:

[0156] In a clean 10 mL Schlenk polymerization tube, 58 mg (1.8 mmol) of elemental sulfur, 281 mg (0.3 mmol) of ketene, 38 mg (0.3 mmol) of 1,4-diisocyanate, and 16.8 mg (0.15 mmol) of DABCO were added. The reaction mixture was evacuated and purged with nitrogen three times. Then, under nitrogen protection, 0.5 mL of dimethyl sulfoxide (DMSO) was added using a syringe. The mixture was heated to 80 °C and stirred for 24 h under sealed conditions. After the reaction was completed, the mother liquor was diluted with 2 mL of DMSO. The resulting solution was then filtered through cotton wool to remove solids. The filtrate was then added dropwise to a 6:1 mixture of methanol and water to settle. Finally, the mixture was allowed to stand, filtered, and dried to obtain the polythiazole compound P10 with a yield of 99%, a weight-average molecular weight of 16,000 g / mol, and a molecular weight distribution of 1.90.

[0157] The fluorescence emission spectrum of polythiazole compound P10 is shown in the figure. Figure 11 Fluorescence emission spectroscopy revealed that the polythiazole compound exhibited fluorescence properties when the substituents of the polyketene were replaced with tetraphenylethylene, demonstrating the diversity of the structure and properties of this type of polymer.

[0158] The GPC curves of the polythiazole compounds P1-P9 prepared in Examples 1-9 are shown below. Figure 9 This indicates that the polythiazole compounds prepared by this method have the advantages of high molecular weight and high yield.

[0159] The refractive index diagrams of the polythiazole compounds P1-P9 prepared in Examples 1-9 are shown below. Figure 10 The high refractive index of this polythiazole compound indicates that this type of polymer has potential applications in the field of optics.

[0160] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0161] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined in this invention may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and technical concepts disclosed herein.

Claims

1. A polythiazole compound, characterized in that, The structural formula is as follows: Among them, R 1 Each is an aryl or aryl derivative; R1 2 R1 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group, R2 2 R2 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group, R3 2 R3 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group, R4 2 R4 3 Each group is an independent carbonyl group or chemical bond, and at least one of them is a carbonyl group; R 4 Independently, it is an aryl group or an aryl derivative; R 5 Independently, it is an alkyl, benzyl, aryl, or aryl derivative; R 6 R 7 Each is an aryl or aryl derivative; n is an integer from 2 to 4000, and the wavy line indicates a repeating polymer unit.

2. The polythiazole compound according to claim 1, characterized in that, R 1 Each is an independent substituted or unsubstituted phenyl group; R 4 Independently, it can be substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted benzophenone, substituted or unsubstituted diphenylmethane, substituted or unsubstituted triphenylamine, or substituted or unsubstituted tetraphenylvinyl. R 5 Alkyl groups with 1-10 carbon atoms, substituted or unsubstituted phenyl groups, substituted or unsubstituted diphenyl ether groups, substituted or unsubstituted diphenyl sulfide groups, substituted or unsubstituted benzophenone groups, substituted or unsubstituted diphenylmethane groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted benzyl groups, substituted or unsubstituted triphenylamino groups, substituted or unsubstituted tetraphenylvinyl groups; R 6 R 7 Each of the following is independently substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted benzophenone, substituted or unsubstituted diphenylmethane, substituted or unsubstituted triphenylamine, or substituted or unsubstituted tetraphenylvinyl. The substituents in substituted phenyl, substituted diphenyl ether, substituted diphenyl sulfide, substituted benzophenone, substituted diphenylmethane, substituted biphenyl, substituted benzyl, substituted triphenylamino, and substituted tetraphenylvinyl are alkyl, alkoxy, hydroxyl, carboxyl, halogen, amino, phenyl, triphenylamino, and tetraphenylvinyl, respectively, with substituents being ... or tetraphenylvinyl, respectively, with substituents being alkyl, alkoxy, hydroxyl, carboxyl, halogen, or tetraphenylvinyl, respectively 3. The method for preparing the polythiazole compound according to any one of claims 1 to 2, characterized in that, Includes the following steps: The polythiazole compounds are obtained by reacting polyene ketone compounds, polyisocyanates and elemental sulfur under the catalysis of an alkali. The structural formula of the polyene ketone compound is: The structural formula of the polyisocyanate compound is as follows:

4. The method for preparing the polythiazole compound according to claim 3, characterized in that, The structural formula of the polyene ketone compound is as follows: The structural formula of the polyisocyanate compound is as follows:

5. The method for preparing the polythiazole compound according to claim 3, characterized in that, The base is one or more of organic and inorganic bases; The organic and inorganic bases include one or more of potassium fluoride, potassium carbonate, cesium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, sodium hydride, triethylenediamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, bis(triphenylphosphine)ammonium chloride, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, and triethylamine.

6. The method for preparing the polythiazole compound according to claim 3, characterized in that, The molar ratio of the polyene ketone compound, polyisocyanate compound, elemental sulfur, and base is 1–20:1–20:1–20:1–15.

7. The method for preparing polythiazole compounds according to claim 3, characterized in that, The reaction temperature is 25–120°C, and the reaction time is 0–36 h, and not 0.

8. The method for preparing polythiazole compounds according to claim 3, characterized in that, The reaction is carried out under a protective gas or in air; The protective gas is one of nitrogen and rare gases.

9. The method for preparing polythiazole compounds according to claim 3, characterized in that, The reaction is carried out in an organic solvent; The organic solvent is one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, hydrocarbon organic solvents, alcohol organic solvents, ester organic solvents, and amide organic solvents; The concentration of the polyenone compound in the organic solvent is 0.01–6.0 mol / L; the concentration of the polyisocyanate compound in the organic solvent is 0.01–6.0 mol / L.

10. The use of the polythiazole compounds according to any one of claims 1 to 2 in the preparation of polymer optoelectronic devices and as refractive materials.

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