Conjugated polythiazole compound as well as preparation method and application thereof

Abstract

The invention discloses a conjugated polythiazole compound as well as a preparation method and application thereof. The compound has structural characteristics as shown in a formula I, a formula II or a formula III, and the preparation method of the compound comprises the following steps: taking a polybasic ketene compound, a diamine compound and elemental sulfur as raw materials, and efficiently synthesizing a target product through a mild reaction in the absence of a catalyst or under an alkaline catalysis condition. Compared with a traditional method, the method has the advantages that the use of dangerous reagents is avoided, the reaction conditions are mild and controllable, the yield is remarkably improved, and in-situ construction of the conjugated polythiazole compound can be realized. The prepared conjugated polythiazole compound has the advantages of high molecular weight, excellent photoluminescence characteristic and outstanding high refractive property, and has wide application prospect in the field of photoelectric functional materials.

Description

Technical Field

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

[0002] Conjugated sulfur-containing heterocyclic polymers, due to their unique structural characteristics, not only occupy an important position in nature but also demonstrate outstanding application value in fields such as organic optoelectronic materials, solar cells, and optical materials. However, the structural diversity and variety development of these polymers are severely restricted by the limitations of existing synthetic methods. Therefore, there is an urgent need to develop synthetic strategies that are simple to operate, have mild conditions, and can yield novel sulfur-containing heterocyclic polymers. As an important member of the chalcogen group, sulfur endows polymer materials with unique functional properties due to its outstanding nucleophilicity, high molar refractive index, excellent coordination ability, and variable valence states. Studies have shown that sulfur-containing polymers generally possess high refractive index, significant metal ion adsorption capacity, excellent dielectric properties, and self-healing properties, and have broad application prospects in optoelectronic functional materials, industrial chemicals, and biomedical materials. This has made the introduction of sulfur atoms into the polymer backbone through green and simple methods a current research hotspot. It is worth mentioning that elemental sulfur, as a chemical byproduct, has the advantages of wide availability and low cost, and has been widely used in the preparation of materials such as polythioamides and polythioureas. Among them, multicomponent polymerization has become an important synthetic tool for constructing sulfur-containing polymers due to its advantages such as high reaction efficiency, mild conditions, simple operation, high atom economy and rich product structure.

[0003] 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.

[0004] Patent CN 118420909 A discloses a polythiazole compound, its preparation method, and its applications. This method uses elemental sulfur as a sulfur source to synthesize aliphatic sulfur-containing heterocyclic polymers (polythiazole thiones). However, this method cannot synthesize conjugated polythiazoles. Therefore, this invention explores the synthesis of conjugated sulfur-containing heterocyclic polymers, specifically polythiazoles, by further modifying the third monomer in the reaction and the synthesis method and conditions. Summary of the Invention

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

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] A conjugated polythiazole compound comprising any one of the following structural formulas:

[0008]

[0009] Among them, R 1 Each can be an aryl group or an aryl derivative independently;

[0010] R1 2 R1 3 R2 2 R2 3 R3 2 R3 3 R4 2 R4 3 Each is independently a carbonyl group or a chemical bond, and at least one is a carbonyl group; R 4 Each can be an aryl group or an aryl derivative independently;

[0011] R 5 Each is independently an alkyl, aryl, or aryl derivative; R 6 R 7 Each is independently an aryl or aryl derivative; n is an integer from 2 to 3000, and the wavy line indicates a repeating polymer unit (the number of repeating polymer units is 2 to 3000).

[0012] Preferred, R 1 Each is independently a substituted or unsubstituted phenyl, or a substituted or unsubstituted tetraphenylethylene;

[0013] R 4 Each of these can be independently substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted heteroaryl, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted benzophenone, substituted or unsubstituted diphenylmethane, substituted or unsubstituted triphenylamino, or substituted or unsubstituted tetraphenylvinyl.

[0014] R 5 Each of the following is independently composed of alkyl, 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 biphenyl, substituted or unsubstituted benzyl, substituted or unsubstituted triphenylamino, or substituted or unsubstituted tetraphenylvinyl.

[0015] R 6 R 7 Each of these can be 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.

[0016] 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

[0017] Further preferred embodiments include heteroaryl groups of pyridine, furan, or thiophene; and halogen atoms of fluorine, chlorine, bromine, or iodine.

[0018] The preparation method of the above-mentioned conjugated polythiazole compounds includes the following steps:

[0019] The conjugated polythiazole compounds are obtained by reacting polyene ketone compounds, diamine compounds, and elemental sulfur in the absence of a catalyst or under the catalysis of a base.

[0020] The structural formula of the polyene ketone compound is any one of the following structural formulas:

[0021]

[0022]

[0023] The structural formula of the diamine compound is:

[0024]

[0025] Preferably, the structural formula of the polyene ketone compound is as follows:

[0026]

[0027] The structural formula of the diamine compound is as follows:

[0028]

[0029] Preferably, the base is one or more of organic and inorganic bases;

[0030] 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.

[0031] Preferably, the molar ratio of the ketone functional group of the polyene ketone compound to the amino group of the diamine compound to the elemental sulfur to the base is 1-20:1-20:1-20:0-15.

[0032] More preferably, the molar ratio of the ketone functional group of the polyene ketone compound to the amino group of the diamine compound to the elemental sulfur to the base is 1-20:1-20:1-20:1-15.

[0033] Preferably, the reaction temperature is 25–160°C, and the reaction time is 0–36 h, and not 0.

[0034] Preferably, the reaction is carried out at 25–80°C for 12–24 hours, followed by a reaction at 100–160°C for 12–24 hours.

[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] Preferably, the concentration of the polyene ketone compound in the organic solvent is 0.01–6.0 mol / L; the concentration of the diamine compound in the organic solvent is 0.01–6.0 mol / L.

[0040] Preferably, after the reaction is complete, the reaction solution is diluted, filtered to obtain filtrate, which is then added dropwise to a precipitant 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 conjugated polythiazole compounds are used in the preparation of polymer optoelectronic devices and as refractive materials.

[0045] This invention can yield conjugated polythiazole compounds in the absence of a catalyst or with different catalysts, and in different gas atmospheres.

[0046] The conjugated 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 this invention utilizes a one-pot reaction with elemental sulfur as the sulfur source and without transition metal catalysis to achieve in-situ construction of conjugated sulfur-containing heterocyclic functional polymers. In the initial stage of the reaction, elemental sulfur, under the catalysis of benzylamine, generates a negatively charged sulfide S3. ·- Free radicals. S3 ·- Free radicals react with chalcone via an intermediate transformation process. Benzylamine, exhibiting strong nucleophilicity, attacks the intermediate to generate another separable intermediate. Subsequently, under high temperature conditions (S3... ·- Free radical quenching and benzylamine catalyze the formation of thioanions from elemental sulfur. The thioanions nucleophilically attack the intermediate, which is then oxidized by DMSO and oxygen in the air to thiazole compounds. This method is characterized by mild conditions, high reaction efficiency, high yield, broad substrate coverage, novel product structure, and avoidance of the use of hazardous reagents. It also enables the in-situ construction of conjugated polythiazole compounds.

[0049] (2) The preparation method of the present invention can obtain conjugated polythiazole compounds with high yield and high molecular weight, without the need for additional metal catalysts, 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 conjugated polythiazole compounds to aromatic heterocyclic amines such as pyridine amine, furan amine and thiophene amine, thereby preparing conjugated polythiazole compounds with various aromatic ring structures. At the same time, the substrate functional groups have high tolerance and can be connected to various functional groups on the aromatic ring to prepare polymer materials with diverse functions.

[0051] (4) The conjugated 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 proton NMR spectra (A) and carbon NMR spectra (B) of the conjugated polythiazole compounds, the two-sided small molecule thiazole compounds, the diene ketone, and the benzylamine in deuterated chloroform of Example 1.

[0053] Figure 2 The image shows a comparison of the infrared absorption spectra of conjugated polythiazole compounds, thiazole compounds with two-sided small molecules, diene ketones, and diamines in Example 1.

[0054] Figure 3 Thermogravimetric curves (A) and refractive index diagrams (B) of the conjugated polythiazole compounds P1-P8 prepared in Examples 1-8 under a nitrogen atmosphere.

[0055] Figure 4 The GPC curves are for the conjugated polythiazole compounds P1-P8 prepared in Examples 1-8.

[0056] Figure 5 The image shows the 1H NMR spectrum of the conjugated polythiazole compound P2 prepared in deuterated chloroform in Example 2.

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

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

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

[0060] Figure 9 The image shows the 1H NMR spectrum of the conjugated polythiazole compound P4 prepared in deuterated chloroform in Example 4.

[0061] Figure 10 The image shows the carbon NMR spectrum of the conjugated polythiazole compound P4 prepared in deuterated chloroform in Example 4.

[0062] Figure 11 The fluorescence emission spectra of the conjugated polythiazole compounds P1-P5 prepared in Examples 1-5 are shown.

[0063] Figure 12 The fluorescence spectra and luminescence intensity diagrams of the conjugated polythiazole compound P3 prepared in Example 3 in different solvents are shown. Detailed Implementation

[0064] 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.

[0065] In the examples, the alkyl chains in the structural formulas are all straight-chain alkyl groups.

[0066] Example 1

[0067] A conjugated polythiazole compound, the structural formula of which is shown in P1:

[0068]

[0069] It is prepared by the following reaction:

[0070]

[0071] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature (Sabuj Kundu, Org. Biomol. Chem. 2016, 14, 10988-10997); M2 is 1,4-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anage; TBD is 1,5,7-triazabicyclo[4.4.0]decen-5-ene, which is commercially available, and in this example, it was purchased from Anage; DMSO is dimethyl sulfoxide, which is commercially available, and in this example, it was purchased from Anage.

[0072] The preparation steps of the conjugated polythiazole compound P1 are as follows:

[0073] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of 4,4'-dipentyldienone, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of DMSO. Then filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Finally, allow to stand, filter, and dry to obtain the conjugated polythiazole compound P1 with a yield of 89%, a weight-average molecular weight of 15100 g / mol, and a molecular weight distribution of 1.25.

[0074] The 1H NMR spectra of conjugated polythiazole compound P1 and thiazole compound 4 (bilateral small molecule) are as follows: Figure 1 In the A, the carbon NMR spectrum is as follows Figure 1 In B, the infrared absorption spectrum is as follows Figure 2 .

[0075] The infrared spectrum, 1H NMR spectrum, and 1C NMR spectrum of the conjugated polythiazole compound P1 are as follows:

[0076] Infrared spectral data (KBr disk), ν (cm -1):3033,2922,2855,1649,1602,1461,1248,1174,1104,1012,975,839,749,610,540.

[0077] 1H NMR spectrum (400MHz, CDCl3) δ (TMS, ppm): 8.14–7.51 (m, 8H), 7.08–6.67 (m, 8H), 2.61–2.55 (m, 4H), 1.62–1.21 (m, 12H), 0.88–0.79 (m, 6H).

[0078] Carbon NMR spectrum (100MHz, CDCl3) δ (TMS, ppm): 188.69, 168.17, 157.40, 149.64, 134.89, 133.06, 131.58, 130.11, 129.09, 128.64, 127.38, 125.98, 36.09, 31.60, 30.79, 22.61, 14.14.

[0079] The thermogravimetric curve of conjugated polythiazole compound P1 is as follows: Figure 3 In A, the thermal decomposition temperature for a 5% weight loss is 360℃.

[0080] To compare the structure with that of the polymer, a two-sided small molecule of thiazole compound 4 was prepared, the structure of which is shown below:

[0081]

[0082] It is prepared by the following reaction:

[0083]

[0084] 3 is benzylamine, which is commercially available; in this example, it was purchased from Energetic.

[0085] The preparation steps of the thiazole compound bilateral small molecule 4 are as follows:

[0086] In a clean 10 mL Schlenk polymerization tube, add 2.0-6 mmol of elemental sulfur, 0.1-0.01 mmol of 4,4'-dipentyldienone, 1.0-4.0 mmol of benzylamine, and 0.2-2.0 mL of dimethyl sulfoxide (DMSO). Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. After cooling the reaction system to room temperature, add 25 mL of dichloromethane and extract three times. Then, vacuum rotary evaporation and silica gel column separation are performed to obtain the thiazole compound 4, a two-sided small molecule, with a yield of 80%.

[0087] The 1H and 1C NMR spectra of the thiazole compound 4 (a two-sided small molecule) are as follows:

[0088] 1H NMR spectrum (400MHz, CDCl3) δ (TMS, ppm): 8.06–8.04 (m, 4H), 7.64 (d, J = 8.0 Hz, 4H), 7.50–7.48 (m, 10H), 7.09 (d, J = 8.0 Hz, 4H), 2.55 (t, J = 8.0 Hz, 4H), 1.55–1.47 (m, 4H), 1.23–1.17 (m, 8H), 0.79 (t, J = 7.2 Hz, 6H).

[0089] Carbon NMR spectrum (100MHz, CDCl3) δ (TMS, ppm): 189.17, 169.29, 157.08, 149.47, 134.77, 134.47, 133.04, 131.54, 131.14, 130.08, 129.43, 129.21, 128.58, 127.04, 36.09, 31.48, 30.79, 22.50, 14.06.

[0090] Example 2

[0091] A conjugated polythiazole compound, the structural formula of which is shown on P2:

[0092]

[0093] It is prepared by the following reaction:

[0094]

[0095] In this example, M3 is an pentyl-substituted diene, synthesized according to the literature (Sabuj Kundu, Org. Biomol. Chem. 2016, 14, 10988-10997); M2 is 1,5-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decen-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0096] The preparation steps of the conjugated polythiazole compound P2 are as follows:

[0097] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of DMSO. Filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Allow to stand, filter, and dry to obtain the conjugated polythiazole compound P2 (NMR spectrum as shown in Figure 1). Figure 5 The carbon NMR spectrum is as follows: Figure 6 The yield was 82%, the weight-average molecular weight was 15,700 g / mol, and the molecular weight distribution was 1.31.

[0098] Example 3

[0099] A conjugated polythiazole compound, the structure of which is shown on P3:

[0100]

[0101] It is prepared by the following reaction:

[0102]

[0103] In this example, M4 is a tetraphenylethylene-substituted diene, synthesized according to the literature (Sabuj Kundu, Org. Biomol. Chem. 2016, 14, 10988-10997); M2 is 1,4-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decene-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0104] The preparation steps of the conjugated polythiazole compound P3 are as follows:

[0105] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 40 °C and stir for 4-24 h, then react at 140 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of DMSO. Filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Allow to stand, filter, and dry to obtain the conjugated polythiazole compound P3 (NMR spectrum as shown in Figure 1). Figure 7 The carbon NMR spectrum is as follows: Figure 8 The yield was 96%, the weight-average molecular weight was 16,800 g / mol, and the molecular weight distribution was 1.35.

[0106] Example 4

[0107] A conjugated polythiazole compound, the structural formula of which is shown on page 4:

[0108]

[0109] It is prepared by the following reaction:

[0110]

[0111] In this example, M5 is a methyl-substituted diene synthesized according to the literature (Sabuj Kundu, Org. Biomol. Chem. 2016, 14, 10988-10997); M2 is 1,4-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decene-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0112] The preparation steps of the conjugated polythiazole compound P4 are as follows:

[0113] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of DMSO. Filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Allow to stand, filter, and dry to obtain the conjugated polythiazole compound P4 (NMR spectrum as shown in Figure 1). Figure 9 The carbon NMR spectrum is as follows: Figure 10 The yield was 95%, the weight-average molecular weight was 17,500 g / mol, and the molecular weight distribution was 1.36.

[0114] Example 5

[0115] A conjugated polythiazole compound, the structural formula of which is shown on page 5:

[0116]

[0117] It is prepared by the following reaction:

[0118]

[0119] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature (author: Sabuj Kundu, article information: Org. Biomol. Chem. 2016, 14, 10988-10997); M6 is 1,5-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decen-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0120] The preparation steps of the conjugated polythiazole compound P5 are as follows:

[0121] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of dimethyl sulfoxide. Then filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Finally, allow to stand, filter, and dry to obtain the conjugated polythiazole compound P5 with a yield of 88%, a weight-average molecular weight of 13,400 g / mol, and a molecular weight distribution of 1.20.

[0122] Example 6

[0123] A conjugated polythiazole compound, the structural formula of which is shown on page 6:

[0124]

[0125] It is prepared by the following reaction:

[0126]

[0127] In this example, M3 is an pentyl-substituted diene, synthesized according to literature (author: Sabuj Kundu, article information: Org. Biomol. Chem. 2016, 14, 10988-10997); M6 is 1,3-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decene-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0128] The preparation steps of the conjugated polythiazole compound P6 are as follows:

[0129] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Heat the mixture to 40 °C and stir for 4-24 h under sealed conditions, then react at 140 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of DMSO. Filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Allow the mixture to stand, filter, and dry to obtain the conjugated polythiazole compound P6 with a yield of 87%, a weight-average molecular weight of 12,000 g / mol, and a molecular weight distribution of 1.13.

[0130] Example 7

[0131] A conjugated polythiazole compound, the structural formula of which is shown on page 7:

[0132]

[0133] It is prepared by the following reaction:

[0134]

[0135] In this example, M3 is an pentyl-substituted diene, synthesized according to literature (author: Sabuj Kundu, article information: Org. Biomol. Chem. 2016, 14, 10988-10997); M7 is 2,6-bis(aminomethyl)pyridine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decen-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0136] The preparation steps of the conjugated polythiazole compound P7 are as follows:

[0137] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-dibenzylamine, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of dimethyl sulfoxide. Then filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Finally, allow to stand, filter, and dry to obtain the conjugated polythiazole compound P7 with a yield of 93%, a weight-average molecular weight of 15,600 g / mol, and a molecular weight distribution of 1.31.

[0138] Example 8

[0139] A conjugated polythiazole compound, the structural formula of which is shown on page 8:

[0140]

[0141] It is prepared by the following reaction:

[0142]

[0143] In this example, M3 is an pentyl-substituted diene, synthesized according to literature (author: Sabuj Kundu, article information: Org. Biomol. Chem. 2016, 14, 10988-10997); M8 is 2,5-di(aminomethyl)furan and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Anenigma; TBD is 1,5,7-triazabicyclo[4.4.0]decen-5-ene, which is commercially available, and in this example, it was purchased from Anenigma.

[0144] The preparation steps of the conjugated polythiazole compound P8 are as follows:

[0145] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, 0.1-0.9 mmol of 1,4-2,5-di(aminomethyl)furan, and 0.1-0.6 mmol of TBD to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of dimethyl sulfoxide. Then filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Finally, allow to stand, filter, and dry to obtain the conjugated polythiazole compound P8 with a yield of 90%, a weight-average molecular weight of 18,000 g / mol, and a molecular weight distribution of 1.56.

[0146] Example 9

[0147] A conjugated polythiazole compound, the structural formula of which is shown in P1:

[0148]

[0149] It is prepared by the following reaction:

[0150]

[0151] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature (author: Sabuj Kundu, article information: Org. Biomol. Chem. 2016, 14, 10988-10997); M2 is 1,4-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Amex; DMSO is dimethyl sulfoxide, which is commercially available, and in this example, it was purchased from Amex.

[0152] The preparation steps of the conjugated polythiazole compound P1 are as follows:

[0153] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, and 0.1-0.9 mmol of 1,4-dibenzylamine to a clean 10 mL Schlenk polymerization tube. Add 0.5 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and stir for 4-24 h, then react at 80-160 °C for another 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of DMSO. Then filter the resulting solution through cotton wool to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Finally, allow to stand, filter, and dry to obtain the conjugated polythiazole compound P1 with a yield of 88%, a weight-average molecular weight of 18,500 g / mol, and a molecular weight distribution of 1.75.

[0154] Example 10

[0155] A conjugated polythiazole compound, the structural formula of which is shown in P1:

[0156]

[0157] It is prepared by the following reaction:

[0158]

[0159] In this example, M1 is 4,4'-dipentyldienone, synthesized according to literature (author: Sabuj Kundu, article information: Org. Biomol. Chem. 2016, 14, 10988-10997); M2 is 1,4-dibenzylamine and 1 is elemental sulfur, which are commercially available, and in this example, they were purchased from Amex; DMSO is dimethyl sulfoxide, which is commercially available, and in this example, it was purchased from Amex.

[0160] The preparation steps of the conjugated polythiazole compound P1 are as follows:

[0161] Add 0.3-2.0 mmol of elemental sulfur, 0.1-0.9 mmol of diene, and 0.1-0.9 mmol of 1,4-dibenzylamine to a clean 10 mL Schlenk polymerization tube. Add 0.2-2.0 mL of dimethyl sulfoxide (DMSO) using a syringe. Under sealed conditions, heat to 25-80 °C and react with stirring under a nitrogen atmosphere for 4-24 h. Then react at 80-160 °C under a nitrogen atmosphere for 4-24 h. Cool the reaction system to room temperature. After the reaction is complete, dilute the mother liquor with 2-10 mL of dimethyl sulfoxide. Then filter the resulting solution through cotton to remove solids. Add the filtrate dropwise to a 6:1 mixture of methanol and water to settle. Finally, let stand, filter, and dry to obtain the conjugated polythiazole compound P1 with a yield of 85%, a weight-average molecular weight of 17500 g / mol, and a molecular weight distribution of 1.65.

[0162] The fluorescence emission spectra of conjugated polythiazole compounds P1-P5 are shown below. Figure 11 Through fluorescence emission spectroscopy (such as...) Figure 11 As shown in A and B in the figure, it can be seen that P1-P5 all have certain fluorescent properties. The difference in luminescence intensity between P1 and P5 may be due to the more conjugated main chain structure of P1. The fluorescence emission spectra and fluorescence intensity of P3 in different solvents (e.g., ...) Figure 12 As shown in A and B in the figure, it can be seen that when the substituent of the polyenone is replaced with tetraphenylethylene (P3), the conjugated polythiazole compound exhibits enhanced aggregation-induced emission, indicating the diversity of the structure and properties of this type of polymer.

[0163] The GPC curves of the conjugated polythiazole compounds P1-P8 prepared in Examples 1-8 are shown below. Figure 4 This indicates that the conjugated polythiazole compounds prepared by this method have the advantages of high molecular weight and high yield.

[0164] The refractive index diagrams of the conjugated polythiazole compounds P1-P8 prepared in Examples 1-8 are shown below. Figure 3 In the example B, the conjugated polythiazole compound has a high refractive index, with the highest reaching 1.7305, indicating that this type of polymer has potential applications in the field of optics.

[0165] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0166] 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 conjugated polythiazole compound, characterized in that, Includes any of the following structural formulas: Among them, R 1 Each can be an aryl group or an aryl derivative independently; R1 2 R1 3 R2 2 R2 3 R3 2 R3 3 R4 2 R4 3 Each is independently a carbonyl group or a chemical bond, and at least one is a carbonyl group; R 4 Each can be an aryl group or an aryl derivative independently; R 5 Each is independently an alkyl, aryl, or aryl derivative; R 6 R 7 Each can be an aryl group or an aryl derivative independently; n is an integer from 2 to 3000, and the wavy line indicates a repeating polymer unit.

2. The conjugated polythiazole compound according to claim 1, characterized in that, R 1 Each is independently a substituted or unsubstituted phenyl, or a substituted or unsubstituted tetraphenylethylene; R 4 Each of these can be independently substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted heteroaryl, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted benzophenone, substituted or unsubstituted diphenylmethane, substituted or unsubstituted triphenylamino, or substituted or unsubstituted tetraphenylvinyl. R 5 Each of the following is independently composed of alkyl, 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 biphenyl, substituted or unsubstituted benzyl, substituted or unsubstituted triphenylamino, or substituted or unsubstituted tetraphenylvinyl. R 6 R 7 Each of these can be 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 conjugated polythiazole compound according to any one of claims 1 to 2, characterized in that, The following steps are involved: The conjugated polythiazole compounds are obtained by reacting polyene ketone compounds, diamine compounds, and elemental sulfur in the absence of a catalyst or under the catalysis of a base. The structural formula of the polyene ketone compound is any one of the following structural formulas: The structural formula of the diamine compound is:

4. The method for preparing the conjugated 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 diamine compound is as follows:

5. The method for preparing the conjugated 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 conjugated polythiazole compound according to claim 3, characterized in that, The molar ratio of the ketone functional group of the polyene ketone compound to the amino group of the diamine compound to the elemental sulfur to the base is 1-20:1-20:1-20:0-15.

7. The method for preparing the conjugated polythiazole compound according to claim 3, characterized in that, The reaction temperature is 25–160°C, and the reaction time is 0–36 h, and not 0.

8. The method for preparing the conjugated polythiazole compound 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 an inert gas.

9. The method for preparing the conjugated polythiazole compound 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 polyketene compounds in the organic solvent is 0.01–6.0 mol / L; the concentration of the polyamine compounds in the organic solvent is 0.01–6.0 mol / L.

10. The use of the conjugated polythiazole compound according to any one of claims 1 to 2 in the preparation of polymer optoelectronic devices and as a refractive material.

Images