Polythiazolidine compound as well as preparation method and application thereof
The synthesis of thiadiazole polymers through a multi-isocyanide and sulfur reaction addresses the limitations of existing methods by providing a high-yield, environmentally friendly process that produces thermally stable and luminescent polymers with unique side-chain hydroxyl groups.
Patent Information
- Application Number
- CN202510395921.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-07-15
AI Technical Summary
The synthesis method of sulfur-containing heterocyclic polymers in the prior art is limited by limited synthesis methods, making it difficult to achieve the preparation of simple operation, mild reaction and novel product structure.
The polyisonitrile compounds and elemental sulfur are reacted under the catalytic action of elemental selenium or alkali, and then the polyaminooxetane compounds are added to construct polythiazolidinium compounds through a one-pot reaction, avoiding the use of transition metal catalysts and high temperature conditions.
It has achieved efficient and economical preparation of high molecular weight and novel structures of polythiazolidinium compounds, with high refractive index and fluorescence emission properties, and is suitable for photoelectric materials and biomedical materials.
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Figure CN120309946A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic chemistry, and in particular to a polythiazolidine compound and a preparation method and application thereof. Background Art
[0002] Sulfur-containing heterocyclic polymers play an important role in the fields of bioactive materials, medicinal molecules, organic optoelectronic materials, organic solar cells, semiconductor image sensors and high-refractive materials with their unique heterocyclic structure. They are a new type of sulfur-containing polymer materials with broad application prospects. However, their structures and types are currently greatly limited by limited synthesis methods. Therefore, it is urgent to develop a series of new sulfur-containing heterocyclic polymer synthesis methods with simple operation, mild reaction and novel product structure. As a kind of oxygen element, sulfur has the advantages of large atomic radius, high molar refractive index, strong coordination ability and rich redox valence state. Therefore, introducing sulfur into polymers can usually give polymer materials unique properties. Studies have shown that sulfur-containing polymers constructed by introducing sulfur atoms have high refractive index, strong metal ion adsorption ability, dielectric properties and self-healing properties, and have broad application prospects in optoelectronic materials, self-healing materials and biomedical materials. Therefore, how to introduce sulfur atoms into polymers in a simple and environmentally friendly way has gained more and more attention.
[0003] Elemental sulfur (S8) is a common byproduct of the chemical industry. It is abundant, cheap and easy to obtain. It is often used in the preparation of polythioamides, polythioureas and polythioesters. In recent years, S8-based reverse sulfurization has been developed to prepare polysulfides with high sulfur content. Among the many synthetic methods for preparing sulfur-containing polymers, multi-component polymerization has been proven to be a powerful tool for preparing novel sulfur-containing polymers. It has the advantages of high reaction efficiency, mild reaction conditions, simple operation, high atom economy and high structural diversity.
[0004] Therefore, how to find appropriate multi-compounds as polymerization substrates and develop efficient, economical and environmentally friendly methods for constructing sulfur-containing heterocyclic polymers using S8 has become an urgent problem that technicians in this field need to solve. Summary of the invention
[0005] In view of the deficiencies in the prior art, the present invention aims to provide a polythiazolidine compound and a preparation method and application thereof.
[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0007] A polythiazolidine compound, the structural formula is as follows:
[0008]
[0009] Among them, R1 1 、R12 , R1 3 Each independently is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
[0010] R2 1 , R2 2 , R2 3 , R2 4 Each independently is a chemical bond, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
[0011] R 3 , R3 1 , R3 2 , R3 3 , R3 4 Each independently is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
[0012] The substituents in the substituted C1-C30 alkyl group, the substituted C6-C30 aryl group, and the substituted C3-C30 heteroaryl group are one or more, and each independently is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, a phenyl group, or a tetraphenylethylene group;
[0013] n is an integer from 2 to 4000, and the wavy line indicates a repeating polymer unit.
[0014] Preferably, R1 1 , R1 2 , R1 3 Each independently is a substituted or unsubstituted phenyl group or a substituted or unsubstituted furyl group;
[0015] R2 1 , R2 2 , R2 3 , R2 4 Each independently is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 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 biphenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted triphenylamine group, or a substituted or unsubstituted tetraphenylethylene group;
[0016] R 3 , R3 1 , R3 2 , R3 3 , R3 4Each is independently 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 triphenylamine group, a substituted or unsubstituted tetraphenylethylene group;
[0017] The substituents in the substituted or unsubstituted phenyl group, substituted or unsubstituted furyl group, substituted or unsubstituted diphenyl ether group, substituted or unsubstituted diphenyl sulfide group, substituted or unsubstituted benzophenone group, substituted or unsubstituted diphenylmethane group, substituted or unsubstituted biphenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted triphenylamine group, substituted or unsubstituted tetraphenylethylene group are one or more, and each is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, a phenyl group, a tetraphenylethylene group.
[0018] The preparation method of the above polythiazolidine compounds comprises the following steps:
[0019] A polyisocyanide compound and elemental sulfur are subjected to a first reaction under the catalytic action of elemental selenium or a base, and then a polyaminooxetane compound is added for a second reaction to obtain the polythiazolidine compound;
[0020] The structural formula of the polyaminooxetane compound is:
[0021]
[0022] The structural formula of the polyisocyanide compound is:
[0023]
[0024]
[0025] Preferably, the structural formula of the polyaminooxetane compound is as follows:
[0026]
[0027] Preferably, the structural formula of the polyisocyanide compound is as follows:
[0028]
[0029] Preferably, the base is one or more of an organic base and an inorganic base;
[0030] More preferably, the organic base and inorganic base 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(triphenylphosphonium) ammonium chloride, 1,5,7-triazabicyclo(4.4.0)dec-5-ene, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, and triethylamine.
[0031] Preferably, the molar ratio of the polyaminooxetane compound: polyisocyanide compound: elemental sulfur: elemental selenium or base is 1 to 20: 1 to 20: 1 to 20: 1 to 15.
[0032] Preferably, the temperature of the first-step reaction is 25 to 100 °C, and the time of the first-step reaction is 0 to 36 h and not 0.
[0033] Preferably, the temperature of the second-step reaction is 25 to 120 °C, and the time of the second-step reaction is 0 to 36 h and not 0.
[0034] Preferably, the first-step reaction and the second-step reaction are carried out under a protective gas or in air;
[0035] More preferably, the protective gas is one of nitrogen and rare gases (inert gases).
[0036] Preferably, the first-step reaction and the second-step reaction are carried out in an organic solvent;
[0037] More preferably, 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;
[0038] More preferably, the concentration of the polyaminooxetane compound in the organic solvent is 0.01 to 6.0 mol / L; the concentration of the polyisocyanide compound in the organic solvent is 0.01 to 6.0 mol / L.
[0039] Preferably, after the reaction is completed, the reaction solution is diluted, filtered to obtain a filtrate, and then the filtrate is dropped into a precipitating agent for precipitation, and the precipitate is collected and dried to a constant weight.
[0040] More preferably, the reaction solution is diluted with 1 to 4 times the volume of N,N-dimethylformamide or tetrahydrofuran of the volume of the reaction solution.
[0041] More preferably, the precipitating agent is anhydrous ether or a mixed solution of alcohol and aqueous solution in any ratio;
[0042] More preferably, the precipitating agent is anhydrous diethyl ether.
[0043] The application of the above-mentioned polythiazolane compounds as refractive materials, as luminescent materials or as solid polymer electrolyte matrices.
[0044] In the present invention, different catalysts and different gas atmospheres are selected, and polythiazolane compounds can be obtained.
[0045] The polythiazolane compounds of the present invention have high molecular weight, good thermal stability and certain luminescent properties. By introducing special luminescent motifs into the monomers, polymers with aggregation-induced emission characteristics can be synthesized. The fluorescence emission spectrum test shows that they have certain fluorescence emission properties and are expected to become a new type of luminescent polymer material.
[0046] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0047] (1) The preparation method of the present invention uses elemental sulfur as the sulfur source, and develops a new polymerization reaction to realize a one-pot reaction under the condition of no transition metal catalysis, thereby realizing the in-situ construction of a new sulfur-containing heterocyclic polymer; the preparation method has mild conditions, high reaction efficiency, high yield, economic and environmental protection, and can avoid the use of dangerous reagents. It can realize the in-situ construction of polythiazolane compounds, and the prepared polythiazolane compounds have novel structures and unique side-chain hydroxyl structures;
[0048] (2) The preparation method of the present invention can obtain polythiazolane compounds with high molecular weight in high yield, does not require a metal catalyst, and does not require high-temperature reaction conditions, thus effectively reducing the preparation cost. The post-treatment and purification operations of the product are more convenient and thorough, and the preparation process is simplified;
[0049] (3) The preparation method of the present invention can expand the substrates of polythiazolane compounds to aromatic isocyanides and benzyl isocyanide monomers, thereby preparing a variety of polythiazolane compounds with aromatic ring structures and benzyl structures. The substrate functional groups have high tolerance, and each repeating unit of the prepared polythiazolane has two in-situ generated hydroxyl groups. By introducing hydroxyl groups in-situ, polythiazolane compounds with a large functional design space can be prepared, and a new sulfur-containing heterocyclic polymer with aggregation-induced emission characteristics can be obtained by introducing special luminescent motifs into the monomers;
[0050] (4) The polythiazolane compounds of the present invention have high molecular weight, good thermal stability and high refractive index properties. Description of the Drawings
[0051] Figure 11H NMR comparison spectra of the small molecule of the thiazolidine compound, the polythiazolidine compound, the aminooxetane, and the isocyanide in deuterated dimethyl sulfoxide in Example 1; wherein, A is the 1H NMR spectrum of the binary isocyanide in deuterated dimethyl sulfoxide, B is the 1H NMR spectrum of the aminooxetane in deuterated dimethyl sulfoxide, C is the 1H NMR spectrum of the small molecule of the thiazolidine compound model in deuterated dimethyl sulfoxide, and D is the 1H NMR spectrum of the polythiazolidine compound prepared in Example 1 in deuterated dimethyl sulfoxide.
[0052] Figure 2 13C NMR comparison spectra of the small molecule of the thiazolidine compound, the polythiazolidine compound, the aminooxetane, and the isocyanide in deuterated dimethyl sulfoxide in Example 1; wherein, A is the 13C NMR spectrum of the binary isocyanide in deuterated dimethyl sulfoxide, B is the 13C NMR spectrum of the aminooxetane in deuterated dimethyl sulfoxide, C is the 13C NMR spectrum of the small molecule of the thiazolidine compound model in deuterated dimethyl sulfoxide, and D is the 13C NMR spectrum of the polythiazolidine compound prepared in Example 1 in deuterated dimethyl sulfoxide.
[0053] Figure 3 Fourier transform infrared spectra comparison of the small molecule of the thiazolidine compound model and the polythiazolidine compound in Example 1; wherein, A is the infrared absorption spectrum of the small molecule of the thiazolidine compound, and B is the infrared absorption spectrum of the polythiazolidine compound P1.
[0054] Figure 4 Thermogravimetric curve of the polythiazolidine compound P1 prepared in Example 1 under a nitrogen atmosphere, wherein the temperature at a weight loss of 5% is 235 °C.
[0055] Figure 5 1H NMR spectrum of the polythiazolidine compound P2 prepared in Example 2 in deuterated dimethyl sulfoxide.
[0056] Figure 6 13C NMR spectrum of the polythiazolidine compound P2 prepared in Example 2 in deuterated dimethyl sulfoxide.
[0057] Figure 7 1H NMR spectrum of the polythiazolidine compound P6 prepared in Example 6 in deuterated dimethyl sulfoxide.
[0058] Figure 8 13C NMR spectrum of the polythiazolidine compound P6 prepared in Example 6 in deuterated dimethyl sulfoxide.
[0059] Figure 9 GPC curves of the polythiazolidine compounds P1 - P5 prepared in Examples 1 - 5.
[0060] Figure 10 GPC curve diagrams of polythiazolane compounds P6 - P9 prepared in Examples 6 - 9.
[0061] Figure 11 Thermogravimetric curves of polythiazolane compounds P1 - P9 prepared in Examples 1 - 9 under a nitrogen atmosphere.
[0062] Figure 12 Refractive index diagrams of polythiazolane compounds P1 - P4 and P7 - P8 prepared in Examples 1 - 4 and Examples 7 - 8.
[0063] Figure 13 UV absorption spectrum and fluorescence emission spectrum of polythiazolane compound P9 prepared in Example 9.
[0064] Figure 14 Electrochemical impedance spectrum diagram of a solid polymer electrolyte film prepared using the polythiazolane compound P1 prepared in Example 1 as a matrix.
[0065] Figure 15 Reaction formula for preparing polythiazolane compounds and P1, P3, P4, P6, P7, P9 prepared in Examples 1, 3, 4, 6, 7, 9. Detailed implementation manners
[0066] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without any creative work belong to the scope of protection of the present invention.
[0067] Example 1
[0068] A polythiazolane compound, whose structural formula is shown as P1:
[0069]
[0070] It is prepared through the following reaction:
[0071]
[0072] Among them, M1 is 1,4 - diisocyanobenzene, synthesized according to the literature; M2 is N,N-(1,3 - phenylbis(methylene))bis(oxetane - 3 - amine), synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market. In this example, it is purchased from Anyji; elemental selenium can be purchased from the market. In this example, it is purchased from Anyji.
[0073] The preparation steps of the polythiazolane compound P1 are as follows:
[0074] In a clean 10 mL Schlenk polymerization tube, 64 mg (2.0 mmol) of elemental sulfur, 64 mg (0.5 mmol) of 1,4-diisocyanobenzene, and 2 mg (0.025 mmol) of elemental selenium were added. Then, 0.5 mL of N,N-dimethylformamide (DMF) was added by syringe under an air atmosphere. After heating to 60 °C and stirring for 4 h under closed conditions, 124 mg of N,N-(1,3-phenylbis(methylene))bis(oxetane-3-amine) (0.5 mmol) was added to the polymerization tube, and the mixture was stirred for 8 h. After the reaction, the reaction mother liquor was diluted with 2 mL of N,N-dimethylformamide. Then, the resulting solution was filtered through cotton to remove the solids in the solution. Subsequently, the filtrate was dropped into anhydrous ether for precipitation. Finally, it was allowed to stand, filtered, and dried to obtain the polythiazolidine compound P1 with a yield of 90%, a number-average molecular weight of 22,100 g / mol, and a molecular weight distribution of 1.70.
[0075] The 1H NMR spectra of the polythiazolidine compound P1 and the thiazolidine compound model small molecule 3 are as Figure 1 , and the 13C NMR spectra are as Figure 2 , and the infrared absorption spectra are as Figure 3 .
[0076] 1H NMR (400 MHz, DMSO-d6) δ (TMS, ppm): 7.37–7.20 (m, 4H), 6.82–6.65 (m, 4H), 5.16–4.97 (m, 4H), 4.41–4.38 (m, 2H), 3.75–3.47 (m, 6H), 3.27–3.13 (m, 4H).
[0077] 13C NMR (100 MHz, DMSO-d6) δ (TMS, ppm): 158.39, 147.15, 138.53, 129.10, 126.66, 122.40, 61.83, 60.10, 47.99, 29.29.
[0078] The thermogravimetric curve of the polythiazolidine compound P1 is as Figure 4 , and the thermal decomposition temperature at 5% weight loss is 235 °C.
[0079] Among them, the thiazolidine compound model small molecule 3 has the structure shown in 3
[0080]
[0081] It is prepared through the following reaction:
[0082]
[0083] Among them, 1 is elemental sulfur, which can be purchased from the market and is purchased from Aladdin in this example; M1 is 1,4-diisocyanobenzene, synthesized according to the literature; 2 is N-benzyl oxetane-3-amine, synthesized according to the literature; elemental selenium can be purchased from the market and is purchased from Aladdin in this example.
[0084] The preparation steps of the thiazolidine compound small molecule 3 are as follows:
[0085] Add 64 mg (2.0 mmol) of elemental sulfur, 64 mg (0.5 mmol) of 1,4-diisocyanobenzene, and 2 mg (0.025 mmol) of elemental selenium into a clean 10 mL Schlenk polymerization tube. Then, add 1.0 mL of N,N-dimethylformamide with a syringe under an air atmosphere. After heating to 60 °C and stirring for 4 h under a closed condition, add 193 mg of N-benzyl oxetane-3-amine (1.0 mmol) to the polymerization tube and stir for 8 h. After the reaction is completed, add 25 mL of dichloromethane, extract three times, then perform rotary evaporation under vacuum, and then separate by silica gel column to obtain the thiazolidine compound 3 with a yield of 86%.
[0086] Example 2
[0087] A poly-thiazolidine compound, whose structural formula is as shown in P2:
[0088]
[0089] It is prepared through the following reaction:
[0090]
[0091] Among them, M1 is 1,4-diisocyanobenzene, synthesized according to the literature; M3 is N,N-(1,4-phenylenebis(methylene))bis(oxetane-3-amine), synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market and is purchased from Aladdin in this example; elemental selenium can be purchased from the market and is purchased from Aladdin in this example.
[0092] The preparation steps of the poly-thiazolidine compound P2 are as follows:
[0093] In a clean 10 mL Schlenk polymerization tube, add 64 mg (2.0 mmol) of elemental sulfur, 64 mg (0.5 mmol) of 1,4-diisocyanobenzene, and 2 mg (0.025 mmol) of elemental selenium. Then, under an air atmosphere, add 0.5 mL of N,N-dimethylformamide (DMF) using a syringe. After heating to 60 °C and stirring for 4 h under sealed conditions, add 124 mg of N,N-(1,4-phenylenebis(methylene))bis(oxetan-3-amine) (0.5 mmol) to the polymerization tube and stir for 8 h. After the reaction, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide. Then, filter the resulting solution through cotton to remove the solids in the solution. Next, drop the filtrate into anhydrous ether for precipitation. Finally, let it stand, filter, and dry to obtain the polythiazolane compound P2 (the proton nuclear magnetic resonance spectrum is as shown in Figure 5 , and the carbon spectrum is as shown in Figure 6 ). The yield is 67%, the number average molecular weight is 20,000 g / mol, and the molecular weight distribution is 1.44.
[0094] Example 3
[0095] A polythiazolane compound, whose structural formula is as shown in P3:
[0096]
[0097] It is prepared through the following reaction:
[0098]
[0099] Among them, M1 is 1,4-diisocyanobenzene, synthesized according to the literature; M4 is N,N'-((oxy-bis(4,1-phenylene))bis(methylene))bis(oxetan-3-amine), synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market. In this example, it is purchased from Aladdin; elemental selenium can be purchased from the market. In this example, it is purchased from Aladdin.
[0100] The preparation steps of the polythiazolane compound P3 are as follows:
[0101] Add 64 mg (2.0 mmol) of elemental sulfur, 64 mg (0.5 mmol) of 1,4-diisocyanatobenzene, and 2 mg (0.025 mmol) of elemental selenium to a clean 10 mL Schlenk polymerization tube. Then, add 0.5 mL of N,N-dimethylformamide (DMF) with a syringe under air atmosphere, heat to 60°C and stir for 4 hours under sealed conditions, then add 170 mg of N,N'-((oxybis(4,1-phenylene))bis(methylene))bis(oxetane-3-amine) (0.5 mmol) to the polymerization tube and stir for 8 hours. After the reaction, the reaction mother liquor was diluted with 2 mL of N,N-dimethylformamide, and the obtained solution was filtered through cotton to remove the solids in the solution. The filtrate was then added dropwise to anhydrous ether for precipitation, and finally allowed to stand, filtered, and dried to obtain a polythiazolidine compound P3 with a yield of 83%, a number average molecular weight of 7,500 g / mol, and a molecular weight distribution of 1.41.
[0102] Example 4
[0103] A polythiazolidine compound, the structural formula of which is shown in P4:
[0104]
[0105] Prepared by the following reaction:
[0106]
[0107] Among them, M1 is 1,4-diisonitibenzene, which is synthesized according to the literature; M5 is N,N'-(furan-2,5-diylbis(methylene))bis(oxetane-3-amine), which is synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anage; elemental selenium can be purchased from the market, and in this example it was purchased from Anage.
[0108] The preparation steps of the polythiazolidine compound P4 are as follows:
[0109] In a clean 10 mL Schlenk polymerization tube, add 64 mg (2.0 mmol) of elemental sulfur, 64 mg (0.5 mmol) of 1,4-diisocyanobenzene, and 2 mg (0.025 mmol) of elemental selenium. Then, add 0.5 mL of N,N-dimethylformamide (DMF) using a syringe under an air atmosphere. After heating to 60 °C and stirring for 4 h under closed conditions, add 119 mg of N,N'-(furan-2,5-diylbis(methylene))bis(oxetan-3-amine) (0.5 mmol) to the polymerization tube and stir for 8 h. After the reaction is completed, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide. Then, filter the resulting solution through cotton to remove the solids in the solution. Next, drop the filtrate into anhydrous ether for precipitation. Finally, let it stand, filter, and dry to obtain the polythiazolidine compound P4 with a yield of 83%, a number-average molecular weight of 13,800 g / mol, and a molecular weight distribution of 2.17.
[0110] Example 5
[0111] A polythiazolidine compound, the structural formula of which is shown as P5:
[0112]
[0113] It is prepared through the following reaction:
[0114]
[0115] Among them, M6 is 1,4-dibenzyl isocyanide, synthesized according to the literature; M2 is N,N-(1,3-phenylbis(methylene))bis(oxetan-3-amine), synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market and is purchased from Aladdin in this example; elemental selenium can be purchased from the market and is purchased from Aladdin in this example.
[0116] The preparation steps of the polythiazolidine compound P5 are as follows:
[0117] Add 64 mg (2.0 mmol) of elemental sulfur, 78 mg (0.5 mmol) of 1,4-dibenzyl isocyanide, and 2 mg (0.025 mmol) of elemental selenium to a clean 10 mL Schlenk polymerization tube. Then, add 0.5 mL of N,N-dimethylformamide (DMF) with a syringe under air atmosphere, heat to 60 ° C under closed conditions, stir and react for 4 hours, then add 124 mg of N,N-(1,3-phenylbis(methylene))bis(oxetane-3-amine) (0.5 mmol) to the polymerization tube, stir and react for 8 hours. After the reaction is completed, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide, then filter the obtained solution through cotton to remove the solids in the solution, then add the filtrate dropwise to anhydrous ether for precipitation, finally stand, filter, and dry to obtain polythiazolidine compound P5 with a yield of 89%, a number average molecular weight of 10 500 g / mol, and a molecular weight distribution of 1.35.
[0118] Example 6
[0119] A polythiazolidine compound, the structural formula of which is shown in P6:
[0120]
[0121] Prepared by the following reaction:
[0122]
[0123] Among them, M6 is 1,4-dibenzyl isocyanate, which is synthesized according to the literature; M4 is N,N'-((oxybis(4,1-phenylene))bis(methylene))bis(oxetane-3-amine), which is synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market, and in this example it was purchased from Anage; elemental selenium can be purchased from the market, and in this example it was purchased from Anage.
[0124] The preparation steps of the polythiazolidine compound P6 are as follows:
[0125] In a clean 10 mL Schlenk polymerization tube, add 64 mg (2.0 mmol) of elemental sulfur, 78 mg (0.5 mmol) of 1,4-dibenzyl isocyanide, and 2 mg (0.025 mmol) of elemental selenium. Then, add 0.5 mL of N,N-dimethylformamide (DMF) using a syringe under an air atmosphere. After heating to 60 °C and stirring for 4 h under closed conditions, add 170 mg of N,N'-((oxybis(4,1-phenylene))bis(methylene))bis(oxetan-3-amine) (0.5 mmol) to the polymerization tube and stir for 8 h. After the reaction is completed, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide. Then, filter the resulting solution through cotton to remove the solids in the solution. Next, drop the filtrate into anhydrous ether for precipitation. Finally, let it stand, filter, and dry to obtain the polythiazolane compound P6 (the proton nuclear magnetic resonance spectrum is as shown in Figure 7 , and the carbon spectrum is as shown in Figure 8 ). The yield is 80%, the number-average molecular weight is 17,000 g / mol, and the molecular weight distribution is 1.67.
[0126] Example 7
[0127] A polythiazolane compound, whose structural formula is as shown in P7:
[0128]
[0129] It is prepared through the following reaction:
[0130]
[0131] Among them, M7 is a diisocyanide compound, synthesized according to the literature; M2 is N,N-(1,3-phenylenebis(methylene))bis(oxetan-3-amine), synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market. In this example, it is purchased from Aladdin; elemental selenium can be purchased from the market. In this example, it is purchased from Aladdin.
[0132] The preparation steps of the polythiazolane compound P7 are as follows:
[0133] In a clean 10 mL Schlenk polymerization tube, add 64 mg (2.0 mmol) of elemental sulfur, 151 mg (0.5 mmol) of M7 diisocyanide compound, and 2 mg (0.025 mmol) of elemental selenium. Then, add 0.5 mL of N,N-dimethylformamide (DMF) with a syringe under an air atmosphere. After heating to 60 °C and stirring for 4 h under closed conditions, add 124 mg of N,N-(1,3-phenylenebis(methylene))bis(oxetan-3-amine) (0.5 mmol) to the polymerization tube and stir for 8 h. After the reaction is completed, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide. Then, filter the resulting solution through cotton to remove the solids in the solution. Next, drop the filtrate into anhydrous ether for precipitation. Finally, let it stand, filter, and dry to obtain the polythiazolidine compound P7 with a yield of 69%, a number average molecular weight of 6700 g / mol, and a molecular weight distribution of 1.31.
[0134] Example 8
[0135] A polythiazolidine compound, the structural formula of which is shown as P8:
[0136]
[0137] It is prepared through the following reaction:
[0138]
[0139] Among them, M7 is a diisocyanide compound, synthesized according to the literature; M4 is N,N'-((oxybis(4,1-phenylene))bis(methylene))bis(oxetan-3-amine), synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market. In this example, it is purchased from Aladdin; elemental selenium can be purchased from the market. In this example, it is purchased from Aladdin.
[0140] The preparation steps of the polythiazolidine compound P8 are as follows:
[0141] In a clean 10 mL Schlenk polymerization tube, add 64 mg (2.0 mmol) of elemental sulfur, 151 mg (0.5 mmol) of M7 diisocyanide compound, and 2 mg (0.025 mmol) of elemental selenium. Then, under an air atmosphere, add 0.5 mL of N,N-dimethylformamide (DMF) using a syringe. After heating to 60 °C and stirring for 4 h under closed conditions, add 170 mg of N,N'-((oxy-bis(4,1-phenylene))bis(methylene))bis(oxetan-3-amine) (0.5 mmol) to the polymerization tube and stir for 8 h. After the reaction, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide. Then, filter the resulting solution through cotton to remove the solids in the solution. Next, drop the filtrate into anhydrous ether for precipitation. Finally, let it stand, filter, and dry to obtain the polythiazolane compound P8 with a yield of 43%, a number-average molecular weight of 5000 g / mol, and a molecular weight distribution of 1.21.
[0142] Example 9
[0143]
[0144] Among them, M1 is 1,4-diisocyanobenzene, synthesized according to the literature; M8 is a diaminooxetane compound, synthesized according to the literature; 1 is elemental sulfur, which can be purchased from the market. In this example, it is purchased from Aladdin; elemental selenium can be purchased from the market. In this example, it is purchased from Aladdin.
[0145] The preparation steps of the polythiazolane compound P9 are as follows:
[0146] In a clean 10 mL Schlenk polymerization tube, add 64 mg (2.0 mmol) of elemental sulfur, 64 mg (0.5 mmol) of 1,4-diisocyanobenzene, and 2 mg (0.025 mmol) of elemental selenium. Then, under an air atmosphere, add 0.5 mL of N,N-dimethylformamide (DMF) using a syringe. After heating to 60 °C and stirring for 4 h under closed conditions, add 251 mg of M8 monomer (0.5 mmol) to the polymerization tube and stir for 8 h. After the reaction, dilute the reaction mother liquor with 2 mL of N,N-dimethylformamide. Then, filter the resulting solution through cotton to remove the solids in the solution. Next, drop the filtrate into anhydrous ether for precipitation. Finally, let it stand, filter, and dry to obtain the polythiazolane compound P9 with a yield of 88%, a number-average molecular weight of 13300 g / mol, and a molecular weight distribution of 1.60.
[0147] The ultraviolet absorption spectrum and fluorescence emission spectrum of the polythiazolane compound P9 are as Figure 13, through the fluorescence emission spectrum, it is known that when the substituent of the polyamino oxetane is replaced with tetraphenylethylene, the polythiazolane compound has fluorescence properties, indicating the diversity of the structures and properties of such polymers.
[0148] The GPC curves of the polythiazolane compounds P1 - P9 prepared in Examples 1 - 9 are as shown in Figure 9 , Figure 10 , indicating that the polythiazolane compounds prepared by this method have the advantage of high molecular weight.
[0149] The TGA curves of the polythiazolane compounds P1 - P9 prepared in Examples 1 - 9 are as shown in Figure 11 , indicating that the polythiazolane compounds prepared by this method have the advantage of good thermal stability.
[0150] The refractive indices of the polythiazolane compounds P1 - P4 and P7 - P8 prepared in Examples 1 - 4 and Examples 7 - 8 are as shown in Figure 12 , and the polythiazolane compounds have relatively high refractive indices, indicating that such polymers have potential application value in the optical field.
[0151] The electrochemical impedance spectrum of the solid polymer electrolyte film (doped with 50% mass fraction of LiTFSI) prepared with the polythiazolane compound P1 prepared in Example 1 as the matrix is as shown in Figure 14 , indicating that such polymers have a certain ionic conductivity and have the potential to be developed as a solid polymer electrolyte matrix.
[0152] In this specification, each example is described in a progressive manner. Each example focuses on the differences from other examples. For the same or similar parts among the examples, reference can be made to each other.
[0153] The above description of the disclosed examples enables those skilled in the art to implement or use the present invention. Various modifications to these examples will be obvious to those skilled in the art. The general principles defined in the present invention can be implemented in other examples without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these examples shown in the present invention, but will conform to the widest scope consistent with the principles and technical concepts disclosed in the present invention.
Claims
1. A polythiazolidine compound, characterized in that, The structural formula is as follows: Among them, R1 1 , R1 2 , R1 3 are each independently a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; R2 1 、R2 2 、R2 3 、R2 4 Each independently is a chemical bond, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; R 3 、R3 1 、R3 2 、R3 3 、R3 4 Each independently is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; The substituents in the substituted C1-C30 alkyl group, substituted C6-C30 aryl group, and substituted C3-C30 heteroaryl group are one or more, and each is independently 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, or a tetraphenylethylene group; n is an integer from 2 to 4000, and the wavy line indicates the repeating polymer unit.
2. The polythiazolidine compound according to claim 1, wherein R1 1 、R1 2 、R1 3 Each independently is a substituted or unsubstituted phenyl group, a substituted or unsubstituted furyl group; R2 1 、R2 2 、R2 3 、R2 4 Each independently is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 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 biphenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted triphenylamine group, or a substituted or unsubstituted tetraphenylethylene group; R 3 、R3 1 、R3 2 、R3 3 、R3 4 Each independently is 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 diphenyl methane group, a substituted or unsubstituted triphenylamine group, or a substituted or unsubstituted tetraphenylethylene group; The substituents in the substituted or unsubstituted phenyl group, substituted or unsubstituted furyl group, substituted or unsubstituted diphenyl ether group, substituted or unsubstituted diphenyl sulfide group, substituted or unsubstituted benzophenone group, substituted or unsubstituted diphenylmethane group, substituted or unsubstituted biphenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted triphenylamine group, and substituted or unsubstituted tetraphenylethylene group are one or more, and each is independently 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, or a tetraphenylethylene group.
3. The preparation method of the polythiazolane compound according to any one of claims 1 to 2, characterized in that, It includes the following steps: The polyisocyanate compound and elemental sulfur undergo a first reaction under the catalytic action of elemental selenium or a base, and then a polyaminooxetane compound is added to undergo a second reaction to obtain the polythiazolidine compound; The structural formula of the polyaminooxetane compound is: The structural formula of the polyisocyanate compound is:
4. The preparation method of the polythiazolane compound according to claim 3, characterized in that, The structural formula of the polyaminooxetane compound is as follows: The structural formula of the polyisocyanate compound is as follows:
5. The preparation method of the polythiazolidine compound according to claim 3, characterized in that, The base is one or more of an organic base and an inorganic base; The organic base and inorganic base 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(triphenylphosphonium) chloride, 1,5,7-triazabicyclo(4.4.0)dec-5-ene, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, and triethylamine.
6. The preparation method of the polythiazolidine compound according to claim 3, characterized in that, The molar ratio of the polyaminooxetane compound: polyisocyanate compound: elemental sulfur: elemental selenium or base is 1-20: 1-20: 1-20: 1-15.
7. The preparation method of the polythiazolane compound according to claim 3, wherein The temperature of the first reaction is 25-120°C, and the time of the first reaction is 0-36 h and not 0; The temperature of the second reaction is 25-120°C, and the time of the second reaction is 0-36 h and not 0.
8. The method for preparing the polythiazoline compound according to claim 3, wherein The first reaction and the second reaction are carried out under a protective gas or in air; The protective gas is one of nitrogen and noble gases.
9. The preparation method of the polythiazolidine compound according to claim 3, characterized in that, The first reaction and the second reaction are 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 polyaminooxetane 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. Use of the polythiazolane compound according to any one of claims 1 to 2 as a refractive index material, as a luminescent material, or as a solid polymer electrolyte matrix.