A multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, its preparation method and application

Abstract

The present invention discloses a multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, a preparation method thereof and an application thereof. The method is as follows: under an inert gas atmosphere, an internal alkyne monomer, a thioamide monomer, a cobalt catalyst and an additive are dissolved in a solvent, and after sufficient reaction, a reaction solution is obtained; the internal alkyne monomer is a binary internal alkyne compound; after simple filtration, the reaction solution is added to a precipitant for precipitation, and after filtration and drying, a multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer is obtained. The preparation method of the present invention has a rich variety of substrates, which are inexpensive and easily available, the reaction conditions are relatively mild, and the polymerization reaction yield is high; the prepared multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer has a novel structure, excellent thermal stability and morphological stability, and has good post-modification potential; the obtained nitrogen-sulfur-containing fused heterocyclic polymer and its post-modified products have special aggregation-induced emission properties and have unique application values in the fields of lithographic patterning, high refractive index materials and gradient refractive index materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of heteroaromatic polymers, and particularly relates to a polysubstituted nitrogen-sulfur-containing heteroaromatic polymer, a preparation method thereof, and an application thereof. Background Art

[0002] Poly nitrogen-sulfur-containing heteroaromatic is a special functional polymer with good thermal stability and special optoelectronic properties, and has good application potential in optical devices, heat-resistant materials and other aspects. Nitrogen-containing heteroaromatic polymers often exhibit excellent electrical properties: a large number of nitrogen atoms in their structures can provide good electron transport ability; good optical properties: such as high absorption coefficient; high fluorescence quantum efficiency; at the same time, due to the conjugation of the heteroaromatic ring and the coordination of nitrogen, the intermolecular interaction of the polymer chain is enhanced and it has good physical and mechanical properties. Therefore, nitrogen-containing heteroaromatic polymers have a wide range of applications in many fields. Sulfur-containing heteroaromatic polymers also have extensive application advantages, such as excellent thermal stability, high refractive index performance, self-healing property and enhanced dielectric property, etc. The poly nitrogen-sulfur-containing heteroaromatic material combining the two has both the advantages of the two, and thus has great potential in the actual application field.

[0003] However, the types of structural units of the existing nitrogen-sulfur-containing heteroaromatic polymers are still very scarce. The main reason is the lack of a polymerization method that can efficiently prepare polysubstituted nitrogen-sulfur-containing heteroaromatic polymers. The existing synthetic methods for preparing related heteroaromatic polymers often have problems such as complex and cumbersome monomer pre-functionalization processes, long synthetic steps, poor economy, harsh polymerization reaction conditions, low reaction efficiency, etc., and it is difficult to introduce multiple substituents simultaneously.

[0004] Therefore, developing a simple and efficient method for preparing polysubstituted nitrogen-sulfur-containing heteroaromatic polymer materials with unique structures and advanced functions has important value in both academic and industrial fields. Summary of the Invention

[0005] In order to solve the above-mentioned disadvantages and deficiencies of the prior art, the primary object of the present invention is to provide a preparation method of a polysubstituted nitrogen-sulfur-containing heteroaromatic polymer.

[0006] Another object of the present invention is to provide a class of polysubstituted nitrogen-sulfur-containing heteroaromatic polymer materials prepared by using the above method.

[0007] Another object of the present invention is to provide a class of polysubstituted nitrogen-sulfur-containing heteroaromatic polyelectrolytes and S-oxidized polysubstituted nitrogen-sulfur-containing heteroaromatic polymers prepared by using the above method.

[0008] Another object of the present invention is to provide an application of the above polysubstituted nitrogen-sulfur-containing heteroaromatic polymer. The poly nitrogen-sulfur-containing heteroaromatic has unique application value in the field of fluorescence lithography patterning.

[0009] Another object of the present invention is to provide the application of the above-mentioned multi-substituted nitrogen-sulfur-containing fused heterocyclic polymers. The poly-nitrogen-sulfur-containing fused heterocycles have unique application values in the fields of high refractive index materials and gradient refractive index materials.

[0010] The object of the present invention is achieved by the following technical solutions:

[0011] A method for preparing a nitrogen-sulfur-containing fused heterocyclic polymer by polymerizing an internal alkyne and a thioamide, comprising the following steps:

[0012] Disperse the internal alkyne monomer, thioamide monomer, catalyst and additive in a solvent respectively, and react under preset conditions to obtain a reaction solution. This step can be carried out under the protection of an inert gas;

[0013] Add the reaction solution to a precipitant for precipitation. After precipitation, filter and dry to obtain a multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer.

[0014] Optionally, in the method for preparing the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, the solvent is selected from at least one of toluene, dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane and 1,2-dichloroethane;

[0015] Preferably, the precipitant is selected from one or more of n-hexane, methanol, diethyl ether, ethanol and acetone.

[0016] Optionally, in the method for preparing the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, the molar ratio of the thioamide monomer to the internal alkyne monomer is 1:1;

[0017] Preferably, the reaction concentration of the internal alkyne monomer is 0.05 - 0.10 mol / L.

[0018] Optionally, in the method for preparing the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, the inert gas can be nitrogen, argon or other inert gases.

[0019] Optionally, in the method for preparing the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, the reaction concentration of the internal alkyne monomer is 0.05 - 0.10 mol / L;

[0020] Preferably, the reaction concentration of the internal alkyne monomer is 0.05 mol / L. By controlling the reaction concentration of the internal alkyne monomer, gelation can be avoided while ensuring the reaction activity.

[0021] Optionally, in the method for preparing the polysubstituted nitrogen-sulfur fused heterocyclic polymer, the cobalt catalyst is one of cobalt(III) carbonyl diiodide(pentamethylcyclopentadienyl), ruthenium(II) dichloride(p-cymene) dimer, and rhodium(III) dichloride(pentamethylcyclopentadienyl) dimer, and the amount of the catalyst used is 30%-50% of the molar amount of the internal alkyne monomer;

[0022] Preferably, the amount of the cobalt catalyst used is 50%. The activity of the polymerization reaction can be improved by changing the amount of the catalyst.

[0023] Optionally, in the method for preparing the polysubstituted nitrogen-sulfur fused heterocyclic polymer, the additive includes a first additive and a second additive. The first additive is one of copper(II) acetate anhydrous, sodium acetate, potassium acetate, cesium acetate, zinc acetate dihydrate, and silver acetate, and the amount used is 2.0-3.5 equivalents of the amount of the internal alkyne monomer; the second additive is one of silver hexafluoroantimonate, sodium hexafluoroantimonate, potassium hexafluorophosphate, and sodium hexafluorophosphate, and the amount used is 30 mol%-60% of the amount of the internal alkyne monomer. Preferably, the additive is copper(II) acetate anhydrous and silver hexafluoroantimonate, and the amounts used are 3.0-3.5 equivalents and 55%-60% of the amount of the internal alkyne monomer, respectively.

[0024] Optionally, in the method for preparing the polysubstituted nitrogen-sulfur fused heterocyclic polymer, the preset conditions include: the reaction temperature is 120-140 °C; the reaction time is 1.5 h-24 h.

[0025] Optionally, in the method for preparing the polysubstituted nitrogen-sulfur fused heterocyclic polymer, the structural general formula of the polysubstituted nitrogen-sulfur fused heterocyclic polymer is shown in Formula (1):

[0026]

[0027] The structural general formula of the internal alkyne monomer is shown in Formula (2):

[0028]

[0029] The structural general formula of the thioamide monomer is shown in Formula (3):

[0030]

[0031] wherein x, y, z, and w are integers from 1 to 200; Ar 1 is an aryl group or an aryl derivative; Ar 2 is an aryl group or an aryl derivative; R is an aryl group, an aryl derivative, or an aliphatic substituent.

[0032] Optionally, the method for preparing the polysubstituted nitrogen-sulfur fused heterocyclic polymer, wherein: Ar 1 is an aryl or aryl derivative, and Ar 2 is an aryl or aryl derivative; R is an aryl, aryl derivative or aliphatic substituent;

[0033] Wherein, the Ar 1 is selected from any one of the following structural formulas 1-23; the Ar 2 is selected from any one of the following structural formulas 24-28;

[0034]

[0035] * is the connection point; wherein, m and n are integers from 1 to 20, and R 1 , R 2 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl, an alkoxy, an allyl or an aryl, and R 3 , R 4 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl, an alkoxy, an allyl, an ester group, a nitro group, a cyano group, an aromatic heterocycle, an aryl; or a bioactive fragment, including but not limited to terpenoids, steroids, fatty alcohols and vitamins, etc.; X is selected from the elements oxygen, sulfur or selenium; Y and Z are the same or different and independently are elements such as carbon, oxygen, nitrogen, sulfur, etc.

[0036] Based on the same inventive concept, the present invention also provides a poly nitrogen-sulfur fused heterocycle, wherein the poly nitrogen-sulfur fused heterocycle is prepared by the preparation method described above.

[0037] Based on the same inventive concept, the present invention also provides an application of the poly nitrogen-sulfur fused heterocycle described above in the field of fluorescence lithography patterning.

[0038] Based on the same inventive concept, the present invention also provides an application of the poly nitrogen-sulfur fused heterocycle described above in the field of high refractive index materials or gradient refractive index materials.

[0039] A method for preparing a polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte, which includes:

[0040] Dissolve the above-mentioned polysubstituted nitrogen-sulfur fused heterocyclic polymer and methyl iodide in dichloromethane, and react at 100 °C to obtain a mixed solution; drop the mixed solution into n-hexane for precipitation to obtain the polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte.

[0041] Optionally, in the method for preparing the polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte, the structural general formula of the polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte is shown in formula (4):

[0042]

[0043] Among them, x, y, z, and w are respectively integers from 1 to 200; Ar 1 is an aryl group or an aryl derivative; Ar 2 is an aryl group or an aryl derivative; R is an aryl group, an aryl derivative, or an aliphatic substituent. Ar 1 is selected from any one of the above-mentioned structural formulas 1 - 23; Ar 2 is selected from any one of the above-mentioned structural formulas 24 - 28; * is the connection point; among them, m and n are integers from 1 to 20, and R 1 , R 2 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group, or an aryl group, and R 3 , R 4 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group, an ester group, a nitro group, a cyano group, an aromatic heterocycle, an aryl group; or a bioactive fragment, including but not limited to terpenoids, steroids, fatty alcohols, and vitamins, etc.; X is selected from the elements oxygen, sulfur, or selenium; Y and Z are the same or different and independently are elements such as carbon, oxygen, nitrogen, sulfur, etc.

[0044] Based on the same inventive concept, the present invention also provides a polysubstituted nitrogen-sulfur-containing fused heterocyclic polyelectrolyte, wherein the polysubstituted nitrogen-sulfur-containing fused heterocyclic polyelectrolyte is prepared by using the above-mentioned preparation method.

[0045] A preparation method of an S-oxidized polysubstituted nitrogen-sulfur-containing fused heterocyclic polymer, which includes:

[0046] Dissolve the above-mentioned polysubstituted nitrogen-sulfur-containing fused heterocyclic polymer and m-chloroperbenzoic acid in dichloromethane, and carry out a reaction at room temperature to obtain a mixed solution; drop the mixed solution into n-hexane for precipitation to obtain the S-oxidized polysubstituted nitrogen-sulfur-containing fused heterocyclic polymer.

[0047] Optionally, in the preparation method of the S-oxidized polysubstituted nitrogen-sulfur-containing fused heterocyclic polymer, the structural general formula of the S-oxidized polysubstituted nitrogen-sulfur-containing fused heterocyclic polymer is shown in formula (5):

[0048]

[0049] Among them, x, y, z, and w are respectively integers from 1 to 200; Ar 1 is an aryl group or an aryl derivative; Ar 2 is an aryl group or an aryl derivative; R is an aryl group, an aryl derivative, or an aliphatic substituent. Ar 1 is selected from any one of the above-mentioned structural formulas 1 - 23; Ar 2is selected from any one of the above structural formulas 24-28; * is a connection point; wherein m and n are integers of 1-20, R 1 , R 2 are the same or different and are independently a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group or an aryl group, R 3 , R 4 The same or different, independently, are hydrogen atoms, halogen atoms, alkylamines, alkyl groups, alkoxy groups, allyl groups, ester groups, nitro groups, cyano groups, aromatic heterocycles, aromatic groups; or biologically active fragments, including but not limited to terpenes, steroids, fatty alcohols and vitamins; X is selected from oxygen, sulfur or selenium; Y and Z are the same or different, independently, are carbon, oxygen, nitrogen, sulfur and other elements.

[0050] Based on the same inventive concept, the present invention also provides an S-oxidized polysubstituted nitrogen-containing sulfur-fused heterocyclic polymer, wherein the S-oxidized polysubstituted nitrogen-containing sulfur-fused heterocyclic polymer is prepared by the above-mentioned preparation method.

[0051] Beneficial effects: Compared with the prior art, the polymerization method of the present invention has a rich variety of substrates, which are cheap and easy to obtain, the reaction conditions are relatively mild, and the polymerization reaction yield is high; the obtained polysubstituted nitrogen-containing sulfur-fused heterocyclic polymer has a novel structure, excellent thermal stability and morphological stability, and the obtained polymer has a high molecular weight (weight average molecular weight is 18,000-29,000, PDI is 1.05-1.50). The polymerization method of the present invention has good economic efficiency, and the catalyst used is a high-yield metal catalyst with high reaction efficiency. The polynitrogen-containing sulfur-fused heterocyclic product of the present invention is easy to separate, and only needs to be precipitated once in a precipitant to obtain a polymer with high purity. The polynitrogen-containing sulfur-fused heterocyclic prepared by the present invention has excellent post-modification ability and can be easily converted into the corresponding polysubstituted nitrogen-containing sulfur-fused heterocyclic polyelectrolyte and S-oxidized polysubstituted nitrogen-containing sulfur-fused heterocyclic polymer. The polynitrogen-containing sulfur-fused heterocyclic prepared by the present invention and its post-modification products have good optical properties and have unique application value in the fields of fluorescent lithography patterning, high refractive index materials and gradient refractive materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is the H NMR spectrum of the polynitrogen-containing sulfur-fused heterocycle P1 obtained in Example 1 in deuterated dichloromethane;

[0053] Figure 2 This is the H NMR spectrum of the polynitrogen-containing sulfur-fused heterocycle P2 obtained in Example 2 in deuterated dichloromethane;

[0054] Figure 3 This is the H NMR spectrum of the polynitrogen-containing sulfur-fused heterocycle P3 obtained in Example 3 in deuterated dichloromethane;

[0055] Figure 41H NMR spectrum of the poly - nitrogen - sulfur heterocyclic P4 obtained in Example 4 in deuterated dichloromethane;

[0056] Figure 5 1H NMR spectrum of the multi - substituted nitrogen - sulfur heterocyclic polyelectrolyte P5 obtained in Example 5 in deuterated dichloromethane;

[0057] Figure 6 1H NMR spectrum of the S - oxidized multi - substituted nitrogen - sulfur heterocyclic polymer P6 obtained in Example 6 in deuterated dichloromethane;

[0058] Figure 7 In the figure, a is the photoluminescence curve of the poly - nitrogen - sulfur heterocyclic P3 obtained in Example 3 in tetrahydrofuran solutions with different diethyl ether contents; b is the aggregation - induced emission curve of the poly - nitrogen - sulfur heterocyclic P3 obtained in Example 3.

[0059] Figure 8 Photolithographic pattern of the poly - nitrogen - sulfur heterocyclic obtained in Example 4;

[0060] Figure 9 Gradient refractive index curves of the polymers P1, P2, P3, P4, P5 and P6 obtained in Examples 1, 2, 3, 4, 5 and 6;

[0061] Figure 10 Gradient refractive index curve of the polymer obtained in Example 4;

[0062] Figure 11 In the figure, a is the photofluorescence curve of the poly - nitrogen - sulfur heterocyclic P5 obtained in Example 5 in tetrahydrofuran solutions with different diethyl ether contents; b is the photoluminescence curve of the poly - nitrogen - sulfur heterocyclic P6 obtained in Example 6 in tetrahydrofuran solutions with different diethyl ether contents. Detailed implementation manners

[0063] The present invention will be further described in detail below in combination with specific examples and drawings. However, the implementation manners of the present invention are not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.

[0064] Example 1

[0065] A preparation method of a nitrogen - sulfur heterocyclic polymer is as follows:

[0066] Dissolve 30.5 mg of 4 - methoxy - N - (methyl(oxo)(phenyl)-λ 647.1 mg of 4-methoxy-N-(methyl(oxo)(phenyl)-λ6-sulfinyl)thiobenzamide, 24.0 mg of 1,6-bis(4-(phenylethynyl)phenoxy)hexane, 54.4 mg of dicarbonyl(η5-pentamethylcyclopentadienyl)cobalt(III) iodide, 18.9 mg of copper(II) acetate and 18.9 mg of silver hexafluoroantimonate were added to 2.0 mL of dry 1,2-dichloroethane and dissolved, and the mixture was stirred at 140 °C for 3 h;

[0067] After the reaction was complete, the reaction mother liquor was diluted with 2 mL of tetrahydrofuran, filtered through a neutral alumina column with a thickness of 2 cm, and directly precipitated in 100 mL of n-hexane solution. The precipitate was collected and dried under vacuum (the drying temperature was 55 °C) to constant weight to obtain a polyheterocyclic compound containing nitrogen and sulfur. The product yield of this example was 87%, the weight-average molecular weight was 24,800 g / mol, and the PDI was 1.17. Among them, 4-methoxy-N-(methyl(oxo)(phenyl)-λ6-sulfinyl)thiobenzamide was prepared according to the literature (Shankar, M.; Saha, A.; Sau, S.; Ghosh, A.; Gandon, V.; Sahoo, A. K. Chem. Sci., 2021, 12, 6393-6405), and 1,6-bis(4-(phenylethynyl)phenoxy)hexane was prepared according to the method disclosed in the literature (Gao, M.; Lam, J. W. Y.; Liu, Y.; Li, J.; Tang, B. Z. Polymer Chemistry 2013, 4(9), 2841-2849.). 6 -sulfinyl)thiobenzamide was prepared according to the literature (Shankar, M.; Saha, A.; Sau, S.; Ghosh, A.; Gandon, V.; Sahoo, A. K. Chem. Sci., 2021, 12, 6393-6405), and 1,6-bis(4-(phenylethynyl)phenoxy)hexane was prepared according to the method disclosed in the literature (Gao, M.; Lam, J. W. Y.; Liu, Y.; Li, J.; Tang, B. Z. Polymer Chemistry 2013, 4(9), 2841-2849.).

[0068] The polyheterocyclic compound containing nitrogen and sulfur obtained in this example has the structural formula shown in P1:

[0069]

[0070] The reaction equation involved in this example is as follows:

[0071]

[0072] The reaction mechanism involved is that this reaction belongs to a C-H activation reaction. First, the cobalt catalyst coordinates with the sulfur atom of the thioamide group to activate the ortho C-H bond, and then the alkyne inserts into the carbon-metal bond to form a seven-membered cyclic active intermediate, followed by reductive elimination to close the ring; then the cobalt catalyst activates the second C-H bond by coordinating with the nitrogen atom of the thioamide, and the same alkyne insertion reaction occurs. Finally, the cobalt catalyst undergoes reductive elimination to close the ring to form a polyheterocyclic compound containing nitrogen and sulfur.

[0073] The 1H NMR spectrum of the polyheterocyclic compound containing nitrogen and sulfur P1 in deuterated dichloromethane in this example is as Figure 1 shown. From Figure 1It can be seen that the solvent peak of deuterated dichloromethane is located at 5.32 ppm. Except for this, the rest are the hydrogen atom signals in the poly-nitrogen-sulfur heterocyclic ring, and the characteristic hydrogen atom signals of several types can also be attributed accordingly. Among them, the characteristic peak of the carbon-hydrogen adjacent to the oxygen atom of the alkyl chain in polymer P1 is at 4.08 - 3.48 ppm, and the peak of other methylene groups in the carbon chain is at 1.92 - 1.38 ppm.

[0074] Example 2

[0075] A preparation method of a poly-nitrogen-sulfur heterocyclic ring polymer is as follows:

[0076] Dissolve 30.5 mg of 4-methoxy-N-(methyl(oxo)(phenyl)-λ 6 -sulfinyl)thiobenzamide, 44.6 mg of N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline, 24.0 mg of carbonyl diiodide(pentamethylcyclopentadienyl)cobalt(III), 54.4 mg of copper(II) acetate and 18.9 mg of silver hexafluoroantimonate in 2.0 mL of dry 1,2-dichloroethane, and stir and react at 140 °C for 3 h;

[0077] After the reaction is complete, dilute the reaction mother liquor with 2 mL of tetrahydrofuran, filter it through a neutral alumina column with a thickness of 2 cm, and directly precipitate it in 100 mL of n-hexane solution. Collect the precipitate and vacuum dry it (the drying temperature is 55 °C) to constant weight to obtain the poly-nitrogen-sulfur heterocyclic ring. The product yield of this example is 98%, the weight-average molecular weight is 18500 g / mol, and the PDI is 1.23. Among them, 4-methoxy-N-(methyl(oxo)(phenyl)-λ 6 -sulfinyl)thiobenzamide is prepared according to the literature (Shankar, M.; Saha, A.; Sau, S.; Ghosh, A.; Gandon, V.; Sahoo, A.K. Chem. Sci., 2021, 12, 6393 - 6405), and N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline is prepared according to the method disclosed in the literature (Gao, M.; Lam, J.W.Y.; Liu, Y.; Li, J.; Tang, B.Z. Polymer Chemistry 2013, 4(9), 2841 - 2849.).

[0078] The poly-nitrogen-sulfur heterocyclic ring obtained in this example has the structural formula shown in P2:

[0079]

[0080] The reaction equation involved in this example is as follows:

[0081]

[0082] The involved reaction mechanism is that this reaction belongs to a C-H activation reaction. First, the cobalt catalyst coordinates with the sulfur atom of the thioamide group to activate the adjacent C-H bond, and then the alkyne inserts into the carbon-metal bond to generate a seven-membered cyclic active intermediate, followed by reductive elimination to form a ring; then the cobalt catalyst activates and coordinates with the nitrogen atom of the thioamide to activate the second C-H bond, and the same alkyne insertion reaction occurs. Finally, the cobalt catalyst undergoes reductive elimination to close the ring and form a nitrogen-sulfur fused heterocycle.

[0083] The hydrogen nuclear magnetic spectrum of the nitrogen-sulfur fused heterocyclic polymer P2 in this example in deuterated dichloromethane is as Figure 2 shown. As can be seen from Figure 2 , the solvent peak and water peak of deuterated dichloromethane are located at 5.32 and 1.56 ppm respectively. Except for these, the rest are the hydrogen atom signals in the nitrogen-sulfur fused heterocycle.

[0084] Example 3

[0085] A preparation method of a nitrogen-sulfur fused heterocyclic polymer is as follows:

[0086] Dissolve 32.1 mg of 4-nitro-N-(methyl(oxo)(phenyl)-λ 6 -sulfinyl)thiobenzamide, 44.6 mg of N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline, 24.0 mg of carbonyl diiodide(pentamethylcyclopentadienyl)cobalt(III), 54.4 mg of copper(II) acetate and 18.9 mg of silver hexafluoroantimonate in 2.0 mL of dry 1,2-dichloroethane, and stir and react at 140 °C for 1 h;

[0087] After the reaction is complete, dilute the reaction mother liquor with 2 mL of tetrahydrofuran, filter it through a neutral alumina column with a thickness of 2 cm, and directly precipitate it in 100 mL of n-hexane solution. Collect the precipitate and vacuum dry it (the drying temperature is 55 °C) to constant weight to obtain the nitrogen-sulfur fused heterocycle. The product yield of this example is 85%, the weight-average molecular weight is 29900 g / mol, and the PDI is 1.50. Among them, 4-nitro-N-(methyl(oxo)(phenyl)-λ 6-Sulfinyl)thiobenzamide was prepared according to the literature (Shankar, M.; Saha, A.; Sau, S.; Ghosh, A.; Gandon, V.; Sahoo, A. K. Chem. Sci., 2021, 12, 6393 - 6405), and N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline was prepared according to the method disclosed in the literature (Gao, M.; Lam, J. W. Y.; Liu, Y.; Li, J.; Tang, B. Z. Polymer Chemistry 2013, 4(9), 2841 - 2849.).

[0088] The polyheterocyclic ring containing nitrogen and sulfur obtained in this example has the structural formula shown in P3:

[0089]

[0090] The reaction equation involved in this example is as follows:

[0091]

[0092] The involved reaction mechanism is that this reaction belongs to a C-H activation reaction. First, the cobalt catalyst coordinates with the sulfur atom of the thioamide group to activate the ortho C-H bond, then the alkyne inserts into the carbon-metal bond to generate a seven-membered ring active intermediate, and reductive elimination occurs to close the ring; then the cobalt catalyst activates and coordinates with the nitrogen atom of the thioamide to activate the second C-H bond, and the same alkyne insertion reaction occurs. Finally, the cobalt catalyst undergoes reductive elimination to close the ring and form a polyheterocyclic ring containing nitrogen and sulfur.

[0093] The hydrogen nuclear magnetic spectrum of the polyheterocyclic ring containing nitrogen and sulfur P3 in deuterated dichloromethane is as Figure 3 shown. The photoluminescence curve of the polyheterocyclic ring containing nitrogen and sulfur P3 in a tetrahydrofuran solution with different diethyl ether contents is as Figure 7 shown. As can be seen from a in Figure 7 , the fluorescence of this polymer gradually increases with the increase of the diethyl ether content and reaches the maximum at 99% diethyl ether content. As can be seen from b in Figure 7 , this polymer exhibits obvious aggregation-induced emission phenomenon.

[0094] Example 4

[0095] A method for preparing a polyheterocyclic ring containing nitrogen and sulfur, the steps are as follows:

[0096] Dissolve 45.1 mg of 4-anthryl-N-(methyl(oxo)(phenyl)-λ 644.6 mg of 4-anthryl-N-(methyl(oxo)(phenyl)-λ-sulfinyl)thiobenzamide, 24.0 mg of N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline, 54.4 mg of dicarbonyl(η5-pentamethylcyclopentadienyl)cobalt(III), 54.4 mg of copper(II) acetate and 18.9 mg of silver hexafluoroantimonate were added to 2.0 mL of dry 1,2-dichloroethane and dissolved, and the mixture was stirred at 140 °C for 3 h;

[0097] After the reaction was complete, the reaction mother liquor was diluted with 2 mL of tetrahydrofuran, filtered through a 2 cm thick neutral alumina column, and directly precipitated in 100 mL of n-hexane solution. The precipitate was collected and dried under vacuum (drying temperature was 55 °C) to constant weight to obtain a polyheterocyclic compound containing nitrogen and sulfur. The product yield of this example was 99%, the weight-average molecular weight was 22,600 g / mol, and the PDI was 1.35. Among them, 4-anthryl-N-(methyl(oxo)(phenyl)-λ-sulfinyl)thiobenzamide was prepared according to the literature (Shankar, M.; Saha, A.; Sau, S.; Ghosh, A.; Gandon, V.; Sahoo, A. K. Chem. Sci., 2021, 12, 6393-6405), and N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline was prepared according to the method disclosed in the literature (Gao, M.; Lam, J. W. Y.; Liu, Y.; Li, J.; Tang, B. Z. Polymer Chemistry 2013, 4(9), 2841-2849.). 6 -sulfinyl)thiobenzamide was prepared according to the literature (Shankar, M.; Saha, A.; Sau, S.; Ghosh, A.; Gandon, V.; Sahoo, A. K. Chem. Sci., 2021, 12, 6393-6405), and N-phenyl-4-(phenylethynyl)-N-(4-(phenylethynyl)phenyl)aniline was prepared according to the method disclosed in the literature (Gao, M.; Lam, J. W. Y.; Liu, Y.; Li, J.; Tang, B. Z. Polymer Chemistry 2013, 4(9), 2841-2849.).

[0098] The polyheterocyclic compound containing nitrogen and sulfur obtained in this example has the structural formula shown in P4:

[0099]

[0100] The reaction equation involved in this example is as follows:

[0101]

[0102] The reaction mechanism involved is that this reaction belongs to a C-H activation reaction. First, the cobalt catalyst coordinates with the sulfur atom of the thioamide group to activate the ortho C-H bond, and then the alkyne inserts into the carbon-metal bond to form a seven-membered cyclic active intermediate, followed by reductive elimination to close the ring; then the cobalt catalyst activates and coordinates with the nitrogen atom of the thioamide to activate the second C-H bond, and the same alkyne insertion reaction occurs. Finally, the cobalt catalyst undergoes reductive elimination to close the ring to form a polyheterocyclic compound containing nitrogen and sulfur.

[0103] The 1H NMR spectrum of the polyheterocyclic compound containing nitrogen and sulfur P4 in deuterated dichloromethane in this example is as Figure 4As shown. The lithography pattern formed by irradiating the film prepared from the nitrogen and sulfur-containing polyheterocyclic P4 with a mercury lamp under the coverage of a photomask is as Figure 8 shown. It can be seen from the figure that the polymer exhibits good light response characteristics and clear patterns can be formed at multiple scales.

[0104] Figure 9 For the gradient refractive index curves of the polymers P1, P2, P3, P4, P5 and P6 obtained in Examples 1, 2, 3 and 4.

[0105] Figure 10 For the refractive index change diagram of the film prepared from the nitrogen and sulfur-containing polyheterocyclic P4 obtained in Example 4 after being irradiated with a mercury lamp for different times. It can be seen from the figure that the polymer shows good refractive index, and at the same time, as the irradiation time prolongs, the refractive index gradually decreases. Therefore, optical materials with multiple refractive indices can be prepared from one kind of polymer.

[0106] Example 5

[0107] A preparation method of a multi-substituted nitrogen and sulfur-containing polyheterocyclic polyelectrolyte is as follows:

[0108] Dissolve 25 mg of the polymer P1 described in Example 1 and 1 mL of methyl iodide in 2.0 mL of dichloromethane, and stir and react at 100 °C for 24 h;

[0109] After the reaction is complete, dilute the reaction mother liquor with 2 mL of tetrahydrofuran, filter it through a neutral alumina column with a thickness of 2 cm, and directly precipitate it in 100 mL of n-hexane solution. Collect the precipitate and vacuum dry (the drying temperature is 55 °C) to constant weight to obtain the multi-substituted nitrogen and sulfur-containing polyheterocyclic polyelectrolyte. The product yield of this example is 92%.

[0110] The multi-substituted nitrogen and sulfur-containing polyheterocyclic polyelectrolyte obtained in this example has the structural formula shown in P5:

[0111]

[0112] The reaction equation involved in this example is as follows:

[0113]

[0114] The hydrogen nuclear magnetic spectrum of the multi-substituted nitrogen and sulfur-containing polyheterocyclic polyelectrolyte P5 in deuterated dichloromethane is as Figure 5 shown. It can be seen from Figure 5 that the solvent peak of deuterated dichloromethane is located at 5.32 ppm. Except for this, all are the hydrogen atom signals in the multi-substituted nitrogen and sulfur-containing polyheterocyclic polyelectrolyte.

[0115] The photoluminescence curve of the multi-substituted nitrogen-sulfur fused heterocyclic polyelectrolyte P5 in tetrahydrofuran solutions with different diethyl ether contents is shown in Figure 11 as shown in a of

[0116] Example 6

[0117] A preparation method of an S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer is as follows:

[0118] Dissolve 50 mg of the polymer P1 described in Example 1 and 50 mL of m-chloroperbenzoic acid in 2.0 mL of dichloromethane, and stir and react at room temperature for 0.5 h;

[0119] After the reaction is complete, dilute the reaction mother liquor with 2 mL of tetrahydrofuran, filter it through a neutral alumina column with a thickness of 2 cm, directly precipitate it in 100 mL of n-hexane solution, collect the precipitate, and vacuum dry (the drying temperature is 55 °C) to constant weight to obtain the S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer. The product yield of this example is 89%.

[0120] The S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer obtained in this example has the structural formula shown in P6:

[0121]

[0122] The reaction equation involved in this example is as follows:

[0123]

[0124] The hydrogen nuclear magnetic spectrum of the S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer P6 in deuterated dichloromethane is shown in Figure 6 as shown. It can be seen from Figure 6 that the solvent peak of deuterated dichloromethane is located at 5.32 ppm. Except for this, all are the hydrogen atom signals in the S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer.

[0125] The photoluminescence curve of the S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer P6 in tetrahydrofuran solutions with different diethyl ether contents is shown in Figure 11 as shown in b of

[0126] In summary, the present invention provides a multi-substituted nitrogen-sulfur-containing heterocyclic polymer, a preparation method thereof, and an application thereof. The method is as follows: under an inert gas atmosphere, an internal alkyne monomer, a thioamide monomer, a cobalt catalyst, and an additive are dissolved in a solvent, and after sufficient reaction, a reaction solution is obtained; the internal alkyne monomer is a binary internal alkyne compound; after simple filtration, the reaction solution is added to a precipitant for precipitation, and after filtration and drying, a multi-substituted nitrogen-sulfur-containing heterocyclic polymer is obtained. The preparation method of the present invention has a rich variety of substrates, which are inexpensive and easily available, the reaction conditions are relatively mild, and the polymerization reaction yield is high; the prepared multi-substituted nitrogen-sulfur-containing heterocyclic polymer has a novel structure, excellent thermal stability and morphological stability, and good post-modification potential; the obtained nitrogen-sulfur-containing heterocyclic polymer and its post-modified products have special aggregation-induced emission properties and have unique application values in the fields of photolithographic patterning, high refractive index materials, and gradient refractive index materials.

Claims

1. A preparation method of a multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, characterized in that, It includes the following steps: Disperse an internal alkyne monomer, a thioamide monomer, a catalyst, and an additive in a solvent respectively, and react under preset conditions to obtain a reaction solution; Add the reaction solution into a precipitant for precipitation, and after precipitation, perform filtration and drying treatments to obtain a polysubstituted nitrogen-sulfur fused heterocyclic polymer; The general structural formula of the polysubstituted nitrogen-sulfur fused heterocyclic polymer is shown in Formula (1): Wherein, x, y, z, and w are integers from 1 to 200 respectively; The general structural formula of the internal alkyne monomer is shown in Formula (2): The general structural formula of the thioamide monomer is shown in Formula (3): Ar 1 is an aryl or aryl derivative; Ar 2 is an aryl or aryl derivative; R is an aryl, aryl derivative or aliphatic substituent; The additive includes a first additive and a second additive. The first additive is one of copper(II) acetate anhydrous, sodium acetate, potassium acetate, cesium acetate, zinc acetate dihydrate, and silver acetate; the second additive is one of silver hexafluoroantimonate, sodium hexafluoroantimonate, potassium hexafluorophosphate, and sodium hexafluorophosphate; The reaction concentration of the internal alkyne monomer is 0.05 - 0.10 mol / L; the dosage of the catalyst is 30% - 50% of the molar dosage of the internal alkyne monomer; the dosage of the first additive is 2.0 - 3.5 equivalents of the dosage of the internal alkyne monomer; The dosage of the second additive is 30 mol% - 60 mol% of the dosage of the internal alkyne monomer; The preset conditions include: the reaction temperature is 120 - 140 °C; the reaction time is 1.5 h - 24 h; The molar ratio of the thioamide monomer to the internal alkyne monomer is 1:1; The catalyst is one of dicarbonyl(η5 - pentamethylcyclopentadienyl)cobalt(III) iodide, dichloro(p - cymene)ruthenium(II) dimer, and dichloro(η5 - pentamethylcyclopentadienyl)rhodium(III) dimer.

2. The preparation method of the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer according to claim 1, characterized in that, The solvent is selected from at least one of toluene, dimethyl sulfoxide, N,N - dimethylformamide, 1,4 - dioxane, and 1,2 - dichloroethane.

3. The preparation method of the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer according to claim 1, characterized in that, The precipitant is selected from one or more of n - hexane, methanol, diethyl ether, ethanol, and acetone.

4. The preparation method of the multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer according to claim 3, characterized in that The Ar 1 is selected from any one of the following structural formulas 1-22; the Ar 2 is selected from any one of the following structural formulas 23-24; * is the connection point; wherein, m and n are integers from 1 to 20; R 1 and R 2 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group or an aryl group; R 3 and R 4 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group, an ester group, a nitro group, a cyano group, an aromatic heterocycle, an aryl group, or a bioactive fragment, and the bioactive fragment includes: terpenoids, steroids, fatty alcohols and vitamins; X is selected from the group consisting of oxygen, sulfur or selenium; Y and Z are the same or different and independently are carbon, oxygen, nitrogen or sulfur.

5. A multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, characterized in that, The polysubstituted nitrogen-sulfur fused heterocyclic polymer is prepared by the preparation method described in any one of claims 1 - 4.

6. A preparation method of a multi-substituted nitrogen-sulfur-containing fused heterocyclic polyelectrolyte, characterized in that, It includes: Dissolve the polysubstituted nitrogen-sulfur fused heterocyclic polymer described in claim 5 and iodomethane in dichloromethane, and react at 25 - 100 °C to obtain a mixed solution; Drop the mixed solution into n - hexane for precipitation to obtain the polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte; The general structural formula of the polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte is shown in Formula (4): wherein, x, y, z, and w are each an integer from 1 to 200; Ar 1 is an aryl or aryl derivative; Ar 2 is an aryl or aryl derivative; R is an aryl, aryl derivative, or aliphatic substituent.

7. The preparation method of the multi-substituted nitrogen-sulfur-containing fused heterocyclic polyelectrolyte according to claim 6, characterized in that, Ar 1 selected from any one of the structural formulas 1-22 described in claim 4; Ar 2 selected from any one of the structural formulas 23-24 in claim 4; * is the connection point; wherein, m and n are integers from 1 to 20, R 1 、R 2 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group or an aryl group, R 3 、R 4 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group, an ester group, a nitro group, a cyano group, an aromatic heterocycle, an aryl group; or a bioactive fragment, including: terpenoids, steroids, fatty alcohols and vitamins; X is selected from the elements oxygen, sulfur or selenium; Y and Z are the same or different and independently are the elements carbon, oxygen, nitrogen or sulfur.

8. A multi-substituted nitrogen-sulfur-containing fused heterocyclic polyelectrolyte, characterized in that, The polysubstituted nitrogen-sulfur fused heterocyclic polyelectrolyte is prepared by the method described in claim 6.

9. A preparation method of an S-oxidized multi-substituted nitrogen-sulfur-containing fused heterocyclic polymer, characterized in that, It includes: Dissolve the polysubstituted nitrogen-sulfur fused heterocyclic polymer described in claim 5 and m - chloroperoxybenzoic acid in dichloromethane, and react at room temperature to obtain a mixed solution; Drop the mixed solution into n - hexane for precipitation to obtain the S - oxidized polysubstituted nitrogen-sulfur fused heterocyclic polymer; The general structural formula of the S - oxidized polysubstituted nitrogen-sulfur fused heterocyclic polymer is shown in Formula (5): wherein, x, y, z, and w are respectively integers from 1 to 200; Ar 1 is an aryl or aryl derivative; Ar 2 is an aryl or aryl derivative; R is an aryl, aryl derivative, or aliphatic substituent.

10. The preparation method of the S-oxidized multi-substituted nitrogen-sulfur fused heterocyclic polymer according to claim 9, characterized in that, The Ar 1 is selected from any one of the structural formulas 1-22 described in claim 4; Ar 2 is selected from any one of the structural formulas 23-24 in claim 4; * is the connection point; wherein, m and n are integers from 1 to 20, and R 1 , R 2 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group or an aryl group, and R 3 , R 4 are the same or different and independently are a hydrogen atom, a halogen atom, an alkylamine, an alkyl group, an alkoxy group, an allyl group, an ester group, a nitro group, a cyano group, an aromatic heterocycle, an aryl group; or a bioactive fragment including terpenoids, steroids, fatty alcohols and vitamins; X is selected from the elements oxygen, sulfur or selenium; Y and Z are the same or different and independently are the elements carbon, oxygen, nitrogen or sulfur.

11. A polysubstituted nitrogen-sulfur fused heterocyclic polymer of S-oxidation type, characterized in that, The S - oxidized polysubstituted nitrogen-sulfur fused heterocyclic polymer is prepared by the method described in claim 9.

12. Use of the polysubstituted nitrogen-sulfur fused heterocyclic polymer according to claim 5 in the preparation of a fluorescent lithographic patterning or gradient refractive material.

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