A bis-Sydney ketone-terminated compound, its preparation method and application

Abstract

This invention relates to a bis-Sydney ketone terminal compound, its preparation method, and its application, belonging to the field of organic synthesis technology. It solves the problems of existing synthetic methods involving multiple reaction steps, low reaction efficiency, low yield, and difficulty in efficiently and massively synthesizing bis-Sydney ketone terminal compounds. The preparation method synthesizes the bis-Sydney ketone terminal compound through a three-step organic reaction, including the following steps: Step 1: Dissolving a primary amino compound, a secondary amination reagent, and a base in a solvent to undergo a secondary amination reaction, followed by recrystallization to obtain a first intermediate; Step 2: Dissolving the first intermediate, adding a hydrolysis reagent to undergo a hydrolysis reaction, adjusting the solution to acidity, and filtering to obtain a second intermediate; Step 3: Dissolving the second intermediate, adding a nitrosating reagent to undergo a nitrosation reaction, adding a dehydrating agent to the reaction system to undergo an internal cyclization reaction, and post-treatment to obtain the bis-Sydney ketone terminal compound.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a novel bis-Sydney ketone-terminated compound, its preparation method, and its application. Background Technology

[0002] Aromatic heterocyclic polymers are a class of special heterocyclic polymers whose molecular backbone contains aromatic benzene rings and heteroatoms such as nitrogen, oxygen, sulfur, and fluorine. Representative aromatic heterocyclic polymers include polyimide, polybenzimidazole, polybenzothiazole, polybenzoxazole, polyquinoxaline, and polypyrrolidone. Due to their unique heteroatoms and cyclic structures, aromatic heterocyclic polymer materials often exhibit excellent properties such as high temperature resistance, radiation resistance, high strength, abrasion resistance, dimensional stability, and high electrical insulation. They are important high-performance polymer materials for extreme environment applications and play an irreplaceable role in many fields such as aerospace and electronics. Therefore, developing new polymerizable monomers and polymerization methods to synthesize new types of aromatic heterocyclic polymers with novel structures and high performance has significant academic and applied value.

[0003] Existing polymerization methods for synthesizing bisysine ketone end-group compounds involve four tandem reactions, resulting in low reaction efficiency and low yield, making it difficult to synthesize bisysine ketone end-group compounds efficiently and in large quantities. Summary of the Invention

[0004] Based on the above analysis, the present invention aims to provide a bis-Sydney ketone terminal compound, its preparation method and application, which solves the problems of existing synthetic methods having many reaction steps, low reaction efficiency, low yield, and difficulty in efficiently and in large quantities synthesizing bis-Sydney ketone terminal compounds.

[0005] The objective of this invention is mainly achieved through the following technical solutions: This invention provides a method for preparing a bis-Sydney ketone terminal compound. The method synthesizes the bis-Sydney ketone terminal compound through a three-step organic reaction, comprising the following steps: Step 1: Dissolve the primary amino compound, secondary amination reagent and base in a solvent to undergo secondary amination reaction, and recrystallize to obtain the i-th intermediate; Step 2: Dissolve the i-th intermediate, add a hydrolysis reagent to initiate a hydrolysis reaction, adjust the solution to be acidic, filter, and obtain the ii-th intermediate; Step 3: Dissolve intermediate ii, add nitrosating agent to induce nitrosation, add dehydrating agent to the reaction system to induce cyclization, and then post-process to obtain bis-Sydney ketone end-group compound.

[0006] Optionally, the molar ratio of the secondary amination reagent to the diprimary amino compound is (2.00~3.00):1.

[0007] Optionally, in step 1, the structure of the diprimary amino compound is shown in formula G below:

[0008] G Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R includes at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0009] Optionally, the secondary amination reagent includes at least one of ethyl bromoacetate, ethyl chloroacetate, tert-butyl bromoacetate, tert-butyl chloroacetate, and methyl bromoacetate.

[0010] Optionally, the secondary amination reaction temperature is 70~80℃ and the reaction time is 3-6h.

[0011] Optionally, in step 2, the hydrolysis reaction temperature is 70~100℃ and the reaction time is 2-6h.

[0012] Optionally, in step 2, the pH of the adjusted solution is 0.5-3.

[0013] Optionally, in step 3, the nitrification reaction is carried out at room temperature for 1-2 hours.

[0014] This invention provides a bis-Sydino ketone-terminated compound, prepared by the above-described method, with the structure shown in the formula DSO:

[0015] Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R includes at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0016] The application of the bisysine ketone end-group compound prepared by the above preparation method or the above-mentioned bisysine ketone end-group compound in the preparation of novel aromatic heterocyclic polymers.

[0017] Compared with the prior art, the present invention can achieve at least the following beneficial effects: ① Traditional bisysine ketone end-group compounds are synthesized by a four-step tandem reaction. The three-step tandem reaction synthesis method in this application is the synthetic route with the fewest steps to date. The yield of each step can reach more than 70%, improving reaction efficiency and overall yield. For example, the overall yield is 64%-81% (e.g., 64.2%-80.6%). It is a highly efficient, high-yield method for the large-scale synthesis of bisysine ketone end-group compounds.

[0018] ② The novel bisysine ketone end-group compounds of this invention have flexible structural designs, and the diverse primary amino reaction starting materials endow the bisysine ketone end-group compounds with diverse chemical structural variability.

[0019] ③The novel bis-Sydionone end-group compound of the present invention is a monomer for synthesizing novel polymers containing pyrazole functional groups. It can undergo unequal stoichiometric stepwise polymerization with benzo[a]cyclo[a]octadiyne] monomers to synthesize a new type of aromatic heterocyclic polymer with designable and regulated structure and function.

[0020] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained from what is particularly pointed out in the description and drawings. Attached Figure Description

[0021] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0022] Figures 1-12 The DSO1-DSO12 prepared for this invention 1 H-NMR spectrum; Figures 13-15 The target products prepared in Examples 1-3 of this invention 1 H NMR spectrum; Figures 16-21 The FT-IR spectrum of the aromatic heterocyclic polymer prepared as an application example of the present invention. Detailed Implementation

[0023] This invention provides a novel method for preparing bis-Sydione terminal compounds. This method synthesizes bis-Sydione terminal compounds through a three-step organic reaction. Compared with existing methods that synthesize bis-Sydione terminal compounds through a four-step tandem reaction, the three-step tandem reaction method of this invention is the synthetic route with the fewest steps to date. The overall yield of the three-step reaction can reach more than 64%, for example, 64.2%-80.6%. It is a highly efficient, high-yield, and large-scale method for synthesizing bis-Sydione terminal compounds.

[0024] The overall synthetic route of this invention is as follows:

[0025] Starting with a diprimary amino compound (G), the amino group is converted into a bis-Sydney ketone group through a series of secondary amination (i), hydrolysis (ii), nitrosation, and internal cyclization reactions (iii), thereby synthesizing the corresponding bis-Sydney ketone end-group compound (DSO).

[0026] Specifically, the preparation method of the present invention includes the following steps: Step 1: Dissolve the primary amino compound, secondary amination reagent and base in a solvent to undergo secondary amination reaction, and recrystallize to obtain the i-th intermediate; Step 2: Dissolve the i-th intermediate, add a hydrolysis reagent to initiate a hydrolysis reaction, adjust the solution to be acidic, filter, and obtain the ii-th intermediate; Step 3: Dissolve intermediate ii, add nitrosating agent to induce nitrosation, add dehydrating agent to the reaction system to induce cyclization, and then post-process to obtain bis-Sydney ketone end-group compound.

[0027] In step 1, the structure of the diprimary amino compound is shown in formula G below:

[0028] G Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R may contain at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0029] Secondary amination reagents include at least one of ethyl bromoacetate, ethyl chloroacetate, tert-butyl bromoacetate, tert-butyl chloroacetate, and methyl bromoacetate.

[0030] The molar ratio of the secondary amination reagent to the diprimary amino compound is (2.00~3.00):1, for example, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, and preferably (2.10~2.50):1.

[0031] The secondary amination reaction temperature is 70~80℃, for example, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃. The reaction time is 3-6h, for example, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h.

[0032] In step 1, the purpose of adding a base is to provide basic conditions for the secondary amination reaction. The molar ratio of the base to the diamine compound is (4.00~6.00):1, for example, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, or 6:1, preferably (4.20~5.00):1.

[0033] The added alkali includes at least one of sodium acetate, potassium acetate, potassium carbonate, and sodium carbonate.

[0034] Specifically, in step 1, the solvent includes at least one of methanol, ethanol, and isopropanol.

[0035] The structure of the i-th intermediate is shown in equation H below:

[0036] H Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R may contain at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0037] In step 2, the solvent for dissolving the i-th intermediate is an organic solvent, including at least one of methanol, ethanol, isopropanol, acetone, and dichloromethane.

[0038] The hydrolysis reagent is sodium hydroxide or hydrochloric acid, and the molar ratio of the hydrolysis reagent to the i-th intermediate is (2.00~4.00):1, for example, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, preferably (2.50~3.50):1.

[0039] The hydrolysis reaction temperature is 70~100℃, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃. The reaction time is 2-6h, for example, 2h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h.

[0040] In step 2, the pH of the solution is adjusted to 0.5-3, for example, 0.5, 1, 1.5, 2, 2.5, 3.

[0041] The structure of the ii intermediate is shown in Equation I below:

[0042] I Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R may contain at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0043] In step 3, the solvent for dissolving the second intermediate is an organic solvent, including at least one of tetrahydrofuran, dichloromethane, trichloromethane, and acetone.

[0044] The nitrifying agent includes at least one selected from tert-butyl nitrite, ethyl bromoacetate, ethyl chloroacetate, tert-butyl bromoacetate, tert-butyl chloroacetate, and methyl bromoacetate. The molar ratio of the nitrifying agent to the intermediate is (2.00~4.00):1, for example, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, or 4:1, preferably (2.50~3.50):1.

[0045] The nitrification reaction is carried out at room temperature for 1-2 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, and 2 hours.

[0046] The dehydrating agent includes at least one of trifluoroacetic anhydride and acetic anhydride. The molar ratio of the dehydrating agent to the intermediate is (2.00~6.00):1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, preferably (2.50~4.50):1.

[0047] The reaction temperature for the internal cyclization reaction is 30–60°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, and 60°C. The reaction time is 2–3 hours, for example, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, and 3 hours.

[0048] In step 3, the post-treatment includes: cooling the reaction solution to room temperature, precipitating the solution in water, filtering, washing the filter cake, and drying. Washing includes sequential washing with deionized water and methanol. The drying temperature is 60–80°C, for example, 60°C, 65°C, 70°C, 75°C, and 80°C. The drying time is 2–8 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 6 hours, 7 hours, and 8 hours.

[0049] The bis-Sydney ketone-terminated compound prepared by the above method contains two Sydney ketone-terminated groups, and its structure is shown in the following formula DSO:

[0050] R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and may contain at least one of functional groups such as ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0051] In addition, the present invention also provides the application of the above-mentioned novel bis-Sydionone end-group compound in the preparation of novel aromatic heterocyclic polymers, wherein a dibenzocyclooctadiyne compound is polymerized with a bis-Sydionone end-group compound prepared by the above method, and a mono-Sydionone compound is used for end-capping treatment to obtain a novel aromatic heterocyclic polymer.

[0052] Specifically, it includes the following steps: Step i: Dissolve the bis-Sydney ketone end-group compound and the end-capping agent (mon-Sydney ketone compound) prepared by the above method in a solvent to obtain a mixed solution; Step ii: Add dibenzocyclooctadiyne to the mixed solution from step i to induce a polymerization reaction and obtain the polymerization stock solution; Step iii: The polymerization solution is allowed to settle to obtain a polymer solid, which is then post-processed to obtain a novel aromatic heterocyclic polymer.

[0053] In step i, the bis-Sydney ketone end-group compound has the structure shown in formula DSO:

[0054] Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R may contain at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

[0055] The capping agent is a monosysyl ketone compound with the structure shown in the formula SSO:

[0056] Wherein, R' includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R' includes at least one of functional groups such as hydrogen, carboxyl, nitro, amino, fluorine, ether bond, thioether bond, carbonyl, carbonate group, amide bond, and fluorine.

[0057] In step i, the solvent is one or more of the following organic solvents: amides, pyrrolidones, alcohol ethers, esters, ketones, phenols, and halogenated hydrocarbons, preferably amides, pyrrolidones, ethers, or hydrogen halides. Specifically, it is N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylacetamide, cyclopentanone, etc. γ At least one of butyrolactone and dichlorobenzene.

[0058] Specifically, in the above applications, the polymerization reaction of the dibenzocyclooctadiyne compound and the bisysine ketone end-group compound first utilizes the unequal saturation of functional groups to increase the degree and rate of reaction. Specifically, the molar ratio of the dibenzocyclooctadiyne compound to the bisysine ketone end-group compound is (1.00~1.50):1, for example, 1:1, 1.02:1, 1.05:1, 1.1:1, 1.13:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, 1.5:1. A preferred molar ratio is (1.02~1.20):1.

[0059] Specifically, in the above applications, a mono-Sydney ketone compound is used to end-cap the aromatic heterocyclic polymer; the molar ratio of the mono-Sydney ketone compound to the di-Sydney ketone end-group compound is (0.005~0.50):1, for example, 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.4:1, 0.5:1. A preferred molar ratio is (0.005~0.25):1.

[0060] Specifically, in step ii, the polymerization reaction temperature is -20℃ to 100℃, for example, -20℃, -10℃, 0℃, 10℃, 20℃, 25℃, 30℃, 40℃, 50℃, 70℃, 90℃, and 100℃. Preferably, it is 0℃ to 40℃. The polymerization reaction time is 2-14 hours, for example, 2 hours, 3 hours, 5 hours, 7 hours, 8 hours, 10 hours, 11 hours, 12 hours, 13 hours, and 14 hours.

[0061] In step ii, a dibenzocyclooctadiyne compound is added to the mixed solution from step i at a temperature of -10 ℃ to 10 ℃, for example, -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃.

[0062] In step iii, the settling liquid is a single solvent or a mixed solvent, and the volume ratio of the settling liquid to the mixed original liquid is 5:1 or higher, for example, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, etc.

[0063] When the settling liquid is a single solvent, it includes one of methanol, tetrahydrofuran, water, ethyl acetate, and ethanol.

[0064] When the precipitate is a mixed solvent, it includes one of methanol and tetrahydrofuran, water, ethyl acetate, and ethanol, and the volume ratio of the two is (1~8):1, for example, 1:1, 2:1, 4:1, 6:1, 8:1.

[0065] In step iii, the post-processing includes drying.

[0066] In step ii, the dibenzocyclooctadiyne compound is synthesized through a four-step organic reaction, starting with 5-dibenzocycloheptenone, and proceeding sequentially through ring expansion, enolization, bromination, and dehydrobromide removal reactions to obtain the dibenzocyclooctadiyne compound.

[0067] Alternatively, in step ii, the dibenzocyclooctadiyne compound is synthesized through a five-step organic reaction. Compared with the four-step organic reaction synthesis described above, the five-step organic reaction synthesis in this invention is a highly effective method for synthesizing aryl benzocyclooctadiyne compounds, represented by dibenzocyclooctadiyne, in large quantities with high yield and low cost.

[0068] The five-step organic reaction synthesis route of this invention is as follows:

[0069] Starting with o-aryldiacetonitrile (A) and o-aryldicarboxaldehyde (B), the corresponding aryl cyclooctadiyne compounds were synthesized by sequentially undergoing cyclization coupling (i), hydrolysis (ii), decarboxylation (iii), bromination (iv), and elimination of hydrogen bromide (v).

[0070] Specifically, the preparation method of the present invention includes the following steps: Step a: Dissolve o-aryldiacetonitrile compound (A), o-aryldicarboxaldehyde compound (B) and base in solvent, and allow them to undergo cyclization coupling reaction. Filter to obtain the first intermediate (C). Step b: Dissolve the first intermediate (C), add a hydrolysis reagent to initiate a hydrolysis reaction, and then perform post-processing to obtain the second intermediate (D). Step c: Dissolve the second intermediate (D), add a decarboxylating agent to cause a decarboxylation reaction, and then perform post-processing to obtain the third intermediate (E).

[0071] Step d: Dissolve the third intermediate (E), add an addition reagent to allow an addition reaction to occur, and then perform post-processing to obtain the fourth intermediate (F).

[0072] Step e: Dissolve the fourth intermediate (F), add an elimination reagent to carry out the elimination of hydrogen bromide reaction, and then perform post-treatment to obtain aryl-cyclooctadiyne compounds.

[0073] In step a, the structures of o-aryldiacetonitrile compound A and o-aryldicarboxaldehyde compound B are shown in the following formulas:

[0074] in, and R1 and R2 are at least one of phenyl, substituted phenyl, naphthyl, or substituted naphthyl groups; R1 and R2 are atoms or groups such as hydrogen, ether bond, halogen, alkyl, tertiary amine, or thioether. R1 and R2 can be the same or different, and can be monosubstituted or polysubstituted.

[0075] The molar ratio of o-aryldiacetonitrile compound A to o-aryldicarboxaldehyde compound B is (0.80~1.30):1, for example, 0.80:1, 0.90:1, 1.10:1, 1.20:1, 1.30:1, with a preferred molar ratio of (0.90~1.10):1.

[0076] The reaction temperature for cyclization coupling reactions is -10 to 30°C, for example, -10°C, 0°C, 10°C, 20°C, and 30°C. The reaction time is 1 to 5 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, and 5 hours.

[0077] In step a, the purpose of adding a base is to provide basic conditions for the cyclization coupling reaction. The molar ratio of the base to the o-aryldicarboxaldehyde compound is (0.20~1.00):1, for example, 0.20:1, 0.30:1, 0.40:1, 0.50:1, 0.60:1, 0.70:1, 0.80:1, 0.90:1, 1.00:1, preferably (0.40~0.60):1.

[0078] The added alkali includes at least one of sodium methoxide, sodium ethoxide, sodium hydroxide, sodium hydride, potassium methoxide, potassium ethoxide, and potassium hydroxide.

[0079] Specifically, in step a, the solvent includes at least one of methanol, ethanol, isopropanol, acetonitrile, and tetrahydrofuran.

[0080] The structure of the first intermediate is shown in equation C below:

[0081] in, and R1 and R2 are at least one of phenyl, substituted phenyl, naphthyl, or substituted naphthyl groups; R1 and R2 are atoms or groups such as hydrogen, ether bond, halogen, alkyl, tertiary amine, or thioether. R1 and R2 can be the same or different, and can be monosubstituted or polysubstituted.

[0082] In step b, the solvent for dissolving the first intermediate is a mixed solution of a weak acid and water, wherein the weak acid includes at least one selected from formic acid, acetic acid, propionic acid, trifluoroacetic acid, and trichloroacetic acid, and the volume ratio of the weak acid to water is (0.50~2.00):1, for example, 0.50:1, 1:1, 1.5:1, or 2.00:1. The hydrolysis reagent is a strong acid, including at least one selected from sulfuric acid and hydrochloric acid. The volume ratio of the strong acid to the weak acid is (0.50~2.00):1, for example, 0.50:1, 1:1, 1.5:1, or 2.00:1.

[0083] It should be noted that in step b, the mixed solution of weak acid and water serves two purposes: first, to dissolve the first intermediate; and second, to adjust the hydrolysis temperature.

[0084] The molar ratio of the strong acid to the first intermediate is (2.00~16.00):1, for example, 2.00:1, 4.00:1, 6.00:1, 8.00:1, 10.00:1, 12.00:1, 14.00:1, 16.00:1, with a preferred molar ratio of (6.00~12.00):1.

[0085] In step b, the hydrolysis reaction temperature is 80~160℃, for example, 80℃, 100℃, 120℃, 140℃, 160℃. The reaction time is 2-6h, for example, 2h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h.

[0086] In step b, the post-processing includes diluting the reaction solution with water, filtering, washing the filter cake with water, and drying to obtain intermediate D.

[0087] The structure of the second intermediate is shown in equation D below:

[0088] in, and R1 and R2 are at least one of phenyl, substituted phenyl, naphthyl, or substituted naphthyl groups; R1 and R2 are atoms or groups such as hydrogen, ether bond, halogen, alkyl, tertiary amine, or thioether. R1 and R2 can be the same or different, and can be monosubstituted or polysubstituted.

[0089] In step c, the solvent for dissolving the second intermediate is an organic solvent, including at least one of xylene, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-diethylformamide.

[0090] The decarboxylating agent comprises a metal catalyst and a ligand. The metal catalyst includes at least one of copper hydroxide, cuprous oxide, cuprous bromide, cuprous iodide, and tetra(triphenylphosphine)palladium. The ligand functions to complex with the metal atoms of the metal catalyst to form a complex, catalyzing the decarboxylation reaction. The molar ratio of ligand to metal catalyst is (1.05~1.30):1, for example, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.25:1, 1.30:1, preferably (1.10~1.20):1. The ligand includes at least one of N,N,N',N'-tetramethylethylenediamine, 1,10-o-phenoroline, 2,9-dimethyl-1,10-o-phenoroline, pyridine, and 1,2-bis(diphenylphosphine)ethane. The molar ratio of the metal catalyst to the second intermediate is (0.05~0.30):1, for example, 0.05:1, 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.30:1, and preferably (0.10~0.20):1.

[0091] The decarboxylation reaction temperature is 100~220℃, for example, 100℃, 120℃, 140℃, 160℃, 180℃, 200℃, 220℃. The reaction time is 2-12h, for example, 2h, 4h, 6h, 8h, 10h, 12h.

[0092] In step c, the post-treatment includes: adding water to dilute the reaction solution, adjusting the pH to 1 with concentrated hydrochloric acid, extracting with ethyl acetate, combining the organic phases, concentrating, and filtering with silica gel column.

[0093] The structure of the third intermediate is shown in equation E below:

[0094] in, and R1 and R2 are at least one of phenyl, substituted phenyl, naphthyl, or substituted naphthyl groups; R1 and R2 are atoms or groups such as hydrogen, ether bond, halogen, alkyl, tertiary amine, or thioether. R1 and R2 can be the same or different, and can be monosubstituted or polysubstituted.

[0095] In step d, the solvent for dissolving the third intermediate is an organic solvent, including at least one of dichloromethane, chloroform, carbon tetrachloride, trichloroethane, and carbon disulfide.

[0096] The addition reagent is liquid bromine, and the addition reaction can be carried out under incandescent light. The molar ratio of the addition reagent to the third intermediate is (2.00~4.00):1, for example, 2.00:1, 2.50:1, 3.00:1, 3.50:1, 4.00:1, and preferably (2.20~3.00):1.

[0097] The reaction temperature for the addition reaction is 25~100℃, for example, 25℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃. The reaction time is 1-12h, for example, 1h, 2h, 4h, 6h, 8h, 10h, 12h.

[0098] In step d, the post-treatment includes: cooling the reaction solution to room temperature, adding a saturated sodium sulfite aqueous solution, stirring thoroughly, allowing it to stand and separate, collecting the organic phase, and removing the solvent by rotary evaporation.

[0099] The structure of the fourth intermediate is shown in equation F below:

[0100] in, and R1 and R2 are at least one of phenyl, substituted phenyl, naphthyl, or substituted naphthyl groups; R1 and R2 are atoms or groups such as hydrogen, ether bond, halogen, alkyl, tertiary amine, or thioether. R1 and R2 can be the same or different, and can be monosubstituted or polysubstituted.

[0101] In step e, the solvent for dissolving the fourth intermediate is an organic solvent, including at least one of diethyl ether, dichloromethane, carbon tetrachloride, tetrahydrofuran, dioxane, methanol, and ethanol.

[0102] The eliminator is a base, which may be at least one of sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, and potassium hydroxide. The molar ratio of the eliminator to the fourth intermediate is (4.00~8.00):1, for example, 4.00:1, 5.00:1, 6.00:1, 7.00:1, 8.00:1, preferably (4.50~6.50):1.

[0103] The elimination reaction temperature is 0~30℃, for example, 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃. The reaction time is 0.5-5h, for example, 0.5h, 1.0h, 2.0h, 3.0h, 4.0h, 5.0h.

[0104] In step e, the post-treatment includes: quenching the reaction solution with water, extraction, concentration of the organic phase, and silica gel column filtration.

[0105] The aryl-denosyl-octadiyne compounds prepared by the above method have the following structures:

[0106] in, and R1 and R2 are at least one of phenyl, substituted phenyl, naphthyl, or substituted naphthyl groups; R1 and R2 are atoms or groups such as hydrogen, ether bond, halogen, alkyl, tertiary amine, or thioether. R1 and R2 can be the same or different, and can be monosubstituted or polysubstituted.

[0107] Compared with the existing four-step organic reaction synthesis of dibenzocyclooctadiyne compounds, the five-step organic reaction synthesis method of the present invention can achieve at least one of the following beneficial effects: ① The traditional method for synthesizing dibenzocyclooctadiyne consists of four organic reactions: ring expansion, enolization, bromination, and removal of hydrogen bromide. The first step, ring expansion, requires a trimethylsilyldiazomethane reagent, which is unstable, easily decomposes to produce highly toxic gases, and is unsafe and expensive to use in large quantities. Furthermore, the overall yield of the four-step reaction is less than 25%, resulting in low productivity. The five-step organic reaction synthesis method of this invention requires inexpensive and readily available reagents, is highly safe, and achieves an overall yield of over 50%, for example, 50.5%-52.2%. It is a highly efficient method for the large-scale synthesis of dibenzocyclooctadiyne compounds with high yield and low cost.

[0108] ② Traditional methods for synthesizing dibenzocyclooctadiyne use 5-dibenzocycloheptenone as a starting material and are only applicable to the synthesis of single-structure dibenzocyclooctadiyne compounds. They cannot be extended to the synthesis of aryl benzocyclooctadiyne compounds other than those with simple benzene rings. The novel synthetic method in this invention uses o-aryl dicarboxaldehydes and o-aryl diacetonitrs as starting materials. Their diverse aryl structures allow this new method to be extended to the synthesis of benzocyclooctadiyne compounds with different aryl or substituted aryl groups, effectively expanding the structural diversity of aryl benzocyclooctadiyne compounds.

[0109] ③ The novel aryl cyclooctadiyne compounds of the present invention are monomers for synthesizing novel polymers containing five-membered heterocyclic functional groups (e.g., triazole and pyrazole). They can undergo unequal stoichiometric stepwise polymerization with monomers such as diazid or bis-Sydione terminal groups to synthesize a class of novel aromatic heterocyclic polymers whose structure and function can be designed and controlled.

[0110] In step i, the end-capping agent monosydiketone compound is synthesized through a four-step organic reaction. Starting with a primary amino compound, the amino group is converted to a sydiketone groups via secondary amination, hydrolysis, nitration, and internal cyclization reactions, thus obtaining the corresponding monosydiketone compound. The primary amino compound used to prepare the monosydiketone compound is a monoamine or diamine monomer, for example, including at least one of aromatic amines, aliphatic amines, semi-aromatic amines, spirocyclic amines, and heterocyclic amines.

[0111] The preparation method described above can achieve at least one of the following beneficial effects: ① The novel aromatic heterocyclic polymer of this invention has a flexible structural design, and the variety of reactive monomers endows the polymer with diverse physicochemical properties. The target product can be obtained directly by solution polymerization, and the good solubility gives it a variety of different sample morphologies, which makes it possible for applications in different fields such as electronics, microelectronics, energy, display, aviation, and aerospace.

[0112] ② This invention utilizes a novel stepwise polymerization method based on self-accelerating chemical reactions, solving the problems of harsh conditions, external catalysts, and numerous side reactions inherent in traditional stepwise condensation reactions, and eliminating the requirement for equivalence of functional groups. The polymerization of dibenzocyclooctadiyne compounds and bis-Sydione-terminated compounds does not require equivalence of functional groups, does not require external catalysts, exhibits mild synthesis conditions, and has no side reactions.

[0113] ③ Traditional stepwise polymerization methods are not easy to synthesize high molecular weight polymers. The new polymerization method provided by this invention utilizes the unequal saturation of functional groups to increase the degree of reaction and accelerate the polymerization rate, which can quickly synthesize high molecular weight aromatic heterocyclic polymers with molecular weights as high as tens of thousands to hundreds of thousands.

[0114] ④ In the preparation method of novel aromatic heterocyclic polymers, the molecular weight of the polymer can be further controlled by adding different proportions of mono-silicon compounds, and the end groups of the polymer can be functionalized by using monofunctional compounds to introduce active sites that can be further reacted.

[0115] This invention provides a novel aromatic heterocyclic polymer prepared by the above-described method. Its molecular structure contains a benzo[a]cyclo[octylpyrazole] characteristic unit, and its terminal functional group R' can be designed and controlled. The general molecular formula is shown below:

[0116] Wherein, R and R' are each independently selected from at least one of aromatic, aliphatic, semi-aromatic, spirocyclic, and heterocyclic structures, and R contains at least one of ether, thioether, carbonyl, carbonate, amide, and fluorine elements, and R' contains at least one of functional groups such as hydrogen, carboxyl, nitro, amino, fluorine, ether, thioether, carbonyl, carbonate, amide, and fluorine elements; n is an integer from 10 to 300, for example, 10, 20, 50, 80, 100, 120, 140, 150, 180, 200, 230, 250, 260, 280, 300, preferably an integer from 20 to 100.

[0117] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The following embodiments select representative diprimary amine reactants, solvents, etc., and synthesize bis-Sydney ketone terminal compounds with different structures using the preparation method provided by the present invention. When the diprimary amine reactants, solvents, etc., in the embodiments are replaced with other types described in the present invention, and the bis-Sydney ketone terminal compounds prepared using the technical methods and conditions provided by the present invention all have the same or similar effects as those in the embodiments. Unless otherwise specified, the raw materials can be obtained from commercially available sources.

[0118] Example 1 Synthesis of the bis-Sydinoketone-terminated compound DSO1

[0119] (i) Diamino compound A1 (80 g), ethyl bromoacetate (102 mL) and sodium acetate (147.65 g) were dissolved in 500 mL of ethanol. After reacting at 80 °C for 3 h, deionized water was added and recrystallized to give compound B1 (140.27 g, 94.2%).

[0120] (ii) Compound B1 (140.27 g) was dissolved in 118 mL of ethanol, and 2 M sodium hydroxide aqueous solution (565 mL) was added. After reacting at 100 °C for 2 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C1 (107.98 g, 90.6%).

[0121] (iii) Compound C1 (107.98 g) was dissolved in 681 mL of acetone, and tert-butyl nitrite (123 mL) was added. After reacting at room temperature for 1 hour, trifluoroacetic anhydride (193 mL) was added, and the reaction was continued at 60 °C for 2 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis(Sydney ketone)-terminated compound DSO1 (92.87 g, 80.4%). The composition of DSO1... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 8.04 (d, 2H), 7.80 (s, 4H), 7.44 (d, 4H) Figure 1 ).

[0122] Example 2 Synthesis of the bis-Sydinoketone-terminated compound DSO2

[0123] (i) Diamino compound A2 (80 g), methyl bromoacetate (59 mL) and potassium carbonate (158.83 g) were dissolved in 312 mL of methanol. After reacting at 80 °C for 4 h, deionized water was added and recrystallized to obtain compound B2 (115.38 g, 93.8%).

[0124] (ii) Compound B8 (115.38 g) was dissolved in 153 mL of ethanol, and 2 M sodium hydroxide aqueous solution (293 mL) was added. After reacting at 90 °C for 5 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C2 (95.17 g, 90.3%).

[0125] (iii) Compound C2 (95.17 g) was dissolved in 545 mL of acetone, and tert-butyl nitrite (71 mL) was added. After reacting at room temperature for 1.25 hours, trifluoroacetic anhydride (120 mL) was added, and the reaction was continued at 45 °C for 2.25 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis(syl)one-terminated compound DSO2 (80.37 g, 80.4%). The DSO2... 1 1H NMR (400 MHz, DMSO-d6) characterization results: δppm: 13.15 (s, 2H), 7.68 (d, 4H), 7.24 (d, 4H), 4.75 (s, 4H) Figure 2 ).

[0126] Example 3 Synthesis of the bis-Sydinoketone-terminated compound DSO3

[0127] (i) Diamino compound A3 (50 g), ethyl bromoacetate (24 mL) and sodium acetate (35.60 g) were dissolved in 161 mL of ethanol. After reacting at 75 °C for 5 h, deionized water was added and recrystallized to give compound B3 (62.74 g, 94.2%).

[0128] (ii) Compound B3 (62.74 g) was dissolved in 68 mL of ethanol, and 2 M sodium hydroxide aqueous solution (145 mL) was added. After reacting at 90 °C for 4 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C3 (51.41 g, 89.2%).

[0129] (iii) Compound C3 (51.41 g) was dissolved in 147 mL of acetone, and tert-butyl nitrite (31 mL) was added. After reacting at room temperature for 1.2 hours, trifluoroacetic anhydride (57 mL) was added, and the reaction was continued at 45 °C for 2.4 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis(syl)one-terminated compound DSO3 (42.61 g, 80.1%). The DSO3... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 8.07-7.94 (m, 4H), 7.76 (s, 2H), 7.52-7.32 (m, 8H), 7.32-7.18 (m, 4H) Figure 3 ).

[0130] Example 4 Synthesis of the bis-Sydinoketone-terminated compound DSO4

[0131] (i) Diamino compound A4 (50 g), methyl bromoacetate (46 mL) and potassium carbonate (134.18 g) were dissolved in 462 mL of methanol. After reacting at 80 °C for 4 h, deionized water was added and recrystallized to obtain compound B4 (81.54 g, 90.8%).

[0132] (ii) Compound B4 (81.54 g) was dissolved in 92 mL of ethanol, and 2 M sodium hydroxide aqueous solution (315 mL) was added. After reacting at 90 °C for 5 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C4 (60.55 g, 86.8%).

[0133] (iii) Compound C4 (58.46 g) was dissolved in 352 mL of acetone, and 46 mL of tert-butyl nitrite was added. After reacting at room temperature for 1.1 hours, trifluoroacetic anhydride (94 mL) was added, and the reaction was continued at 30 °C for 2.2 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis(Sydney ketone)-terminated compound DSO4 (50.73 g, 81.4%). The DSO4... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 7.75 (s, 2H), 7.64 (d, 2H), 7.38 (d, 4H) Figure 4 ).

[0134] Example 5 Synthesis of the bis-Sydinoketone-terminated compound DSO5

[0135] (i) Diamino compound A5 (50 g), ethyl chloroacetate (34 mL) and potassium acetate (62.10 g) were dissolved in 244 mL of ethanol. After reacting at 70 °C for 6 h, deionized water was added and recrystallized to give compound B5 (67.56 g, 95.2%).

[0136] (ii) Compound B5 (67.56 g) was dissolved in 66 mL of ethanol, and 2 M sodium hydroxide aqueous solution (209 mL) was added. After reacting at 80 °C for 6 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C5 (54.09 g, 88.6%).

[0137] (iii) Compound C5 (54.09 g) was dissolved in 147 mL of acetone, and tert-butyl nitrite (35 mL) was added. After reacting at room temperature for 1 hour, acetic anhydride (47 mL) was added, and the reaction was continued at 50 °C for 3 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis-Sydney ketone-terminated compound DSO5 (45.76 g, 81.2%). The DSO5... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 7.98-7.89 (m, 4H), 7.73 (s, 2H), 7.39-7.29 (m, 4H), 7.28-7.20 (m, 4H), 7.13-7.04 (m, 4H), 1.68 (s, 6H) Figure 5 ).

[0138] Example 6 Synthesis of the bis-Sydinoketone-terminated compound DSO6

[0139] (i) Diamino compound A6 (100 g), ethyl bromoacetate (235 mL) and sodium acetate (348.94 g) were dissolved in 1030 mL of ethanol. After reacting at 70 °C for 6 h, deionized water was added and recrystallized to obtain compound B6 (246.51 g, 95.1%).

[0140] (ii) Compound B6 (246.51 g) was dissolved in 355 mL of ethanol, and 2 M sodium hydroxide aqueous solution (1230 mL) was added. After reacting at 100 °C for 3 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C6 (182.78 g, 92.7%).

[0141] (iii) Compound C6 (182.78 g) was dissolved in 1010 mL of acetone, and tert-butyl nitrite (254 mL) was added. After reacting at room temperature for 1.8 hours, trifluoroacetic anhydride (460 mL) was added, and the reaction was continued at 45 °C for 2.7 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis(syl)one-terminated compound DSO6 (172.79 g, 86.1%). The DSO6... 1 1H NMR (400 MHz, DMSO-d6) characterization results: δppm: 8.28 (s, 4H), 7.93 (s, 2H) Figure 6 ).

[0142] Example 7 Synthesis of the bis-Sydinoketone-terminated compound DSO7

[0143] (i) Diamino compound A7 (100 g), ethyl chloroacetate (134 mL) and potassium acetate (255.84 g) were dissolved in 630 mL of ethanol. After reacting at 75 °C for 5 h, deionized water was added and recrystallized to give compound B7 (179.74 g, 96.2%).

[0144] (ii) Compound B7 (179.74 g) was dissolved in 202 mL of ethanol, and 2 M sodium hydroxide aqueous solution (473 mL) was added. After reacting at 100 °C for 3 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C7 (106.74 g, 89.7%).

[0145] (iii) Compound C7 (106.74 g) was dissolved in 565 mL of acetone, and tert-butyl nitrite (102 mL) was added. After reacting at room temperature for 2 hours, acetic anhydride (112 mL) was added, and the reaction was continued at 45 °C for 3 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis-Sydney ketone-terminated compound DSO7 (97.87 g, 85.7%). The DSO7... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 7.83 (d, 2H), 7.75 (s, 2H), 7.18 (d, 4H), 4.09 (s, 2H) Figure 7 ).

[0146] Example 8 Synthesis of the bis-Sydinoketone-terminated compound DSO8

[0147] (i) Diamino compound A8 (100 g), ethyl bromoacetate (111 mL) and sodium carbonate (213.43 g) were dissolved in 576 mL of isopropanol. After reacting at 80 °C for 4 h, deionized water was added and recrystallized to obtain compound B8 (163.58 g, 96.6%).

[0148] (ii) Compound B8 (163.58 g) was dissolved in 182 mL of ethanol, and 2 M sodium hydroxide aqueous solution (428 mL) was added. After reacting at 100 °C for 5 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C8 (126.86 g, 89.5%).

[0149] (iii) Compound C8 (126.86 g) was dissolved in 464 mL of acetone, and tert-butyl nitrite (104 mL) was added. After reacting at room temperature for 1.6 hours, acetic anhydride (137 mL) was added, and the reaction was continued at 50 °C for 2.6 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis-Sydney ketone-terminated compound DSO8 (114.74 g, 85.3%). The composition of DSO8... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: 8.54-8.06 (m, 8H), 7.80 (s, 2H) Figure 8 ).

[0150] Example 9 Synthesis of the bis-Sydinoketone-terminated compound DSO9

[0151] (i) Diamino compound A9 (10 g), ethyl bromoacetate (10 mL) and sodium acetate (14.99 g) were dissolved in 82 mL of ethanol. After reacting at 80 °C for 6 h, deionized water was added and recrystallized to obtain compound B9 (14.25 g, 91.2%).

[0152] (ii) Compound B9 (14.25 g) was dissolved in 35 mL of ethanol, and 2 M sodium hydroxide aqueous solution (45 mL) was added. After reacting at 100 °C for 3 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C9 (12.02 g, 93.8%).

[0153] (iii) Compound C9 (12.02 g) was dissolved in 95 mL of acetone, and tert-butyl nitrite (12 mL) was added. After reacting at room temperature for 1.5 hours, trifluoroacetic anhydride (22 mL) was added, and the reaction was continued at 45 °C for 2.5 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis(Sydney ketone)-terminated compound DSO9 (10.30 g, 80.5%). The DSO9... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δppm: 7.75 (s, 2H), 7.17 (d, 4H), 7.09 (d, 4H), 2.72-2.02 (dd, 2H), 0.91 (s, 12H) Figure 9 ).

[0154] Example 10 Synthesis of the bis-Sydinoketone-terminated compound DSO10

[0155] (i) Diamino compound A10 (40 g), tert-butyl bromoacetate (69 mL) and sodium acetate (77.30 g) were dissolved in 377 mL of ethanol. After reacting at 75 °C for 6 h, deionized water was added and recrystallized to obtain compound B10 (65.25 g, 90.3%).

[0156] (ii) Compound B10 (65.25 g) was dissolved in 95 mL of acetic acid, and 136 mL of 5 M HCl aqueous solution was added. After reacting at 80 °C for 6 h, the reaction solution was precipitated in water and filtered to obtain compound C10 (53.05 g, 95.2%).

[0157] (iii) Compound C10 (53.05 g) was dissolved in 269 mL of acetone, and tert-butyl nitrite (58 mL) was added. After reacting at room temperature for 1 hour, trifluoroacetic anhydride (107 mL) was added, and the reaction was continued at 60 °C for 2 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and the filter cake was dried to obtain the bis-Sydney ketone-terminated compound DSO10 (46.81 g, 82.7%). The composition of DSO10... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 7.94 (d, 4H), 7.75-7.74 (m, 6H) Figure 10 ).

[0158] Example 11 Synthesis of the bis-Sydinoketone-terminated compound DSO11

[0159] (i) Diamino compound A11 (5 g), tert-butyl chloroacetate (9 mL) and sodium acetate (10.08 g) were dissolved in 68 mL of ethanol. After reacting at 70 °C for 5 h, deionized water was added and recrystallized to obtain compound B11 (8.15 g, 95.7%).

[0160] (ii) Compound B11 (8.15 g) was dissolved in 20 mL of acetic acid, and 14 mL of 5 M HCl aqueous solution was added. After reacting at 70 °C for 6 h, the reaction solution was precipitated in water and filtered to obtain compound C11 (6.87 g, 97.5%).

[0161] (iii) Compound C11 (6.87 g) was dissolved in 76 mL of acetone, and tert-butyl nitrite (9 mL) was added. After reacting at room temperature for 2 hours, trifluoroacetic anhydride (16 mL, 6 eq) was added, and the reaction was continued at 35 °C for 2.8 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis-Sydney ketone-terminated compound DSO11 (6.30 g, 86.4%). The composition of DSO11... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 7.81 (d, 4H), 7.75 (s, 2H), 7.15 (d, 4H) Figure 11 ).

[0162] Example 12 Synthesis of the bis-Sydinoketone-terminated compound DSO12

[0163] (i) The diamino compound A12 (10 g), ethyl bromoacetate (9 mL) and sodium acetate (12.79 g) were dissolved in 72 mL of ethanol. After reacting at 80 °C for 6 h, deionized water was added and recrystallized to obtain compound B12 (14.13 g, 94.4%).

[0164] (ii) Compound B12 (14.13 g) was dissolved in 20 mL of acetic acid, and 22 mL of 5 M HCl aqueous solution was added. After reacting at 85 °C for 6 h, the reaction solution was precipitated in water and filtered to obtain compound C12 (12.60 g, 95.7%).

[0165] (iii) Compound C12 (12.60 g) was dissolved in 78 mL of acetone, and tert-butyl nitrite (13 mL) was added. After reacting at room temperature for 2 hours, trifluoroacetic anhydride (22 mL) was added, and the reaction was continued at 45 °C for 2.5 hours. The reaction solution was then cooled to room temperature, precipitated in water, and filtered. The filter cake was washed successively with deionized water and methanol, and dried to obtain the bis-Sydney ketone-terminated compound DSO12 (11.04 g, 83.6%). The DSO12... 1 H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 10.20 (s, 2H), 8.18 (d, 4H), 7.94 (d, 4H), 7.75 (s, 2H), 7.65 (d, 4H) Figure 12 ).

[0166] Comparative Example 1 This comparative example has the same structural formula as the bis-Sydino ketone-terminated compound prepared in Example 1, and was synthesized using a conventional four-step tandem reaction. The overall synthetic route is as follows:

[0167] (i) Diamino compound A1 (80 g), ethyl bromoacetate (102 mL) and sodium acetate (147.65 g) were dissolved in 500 mL of ethanol. After reacting at 80 °C for 3 h, deionized water was added and recrystallized to give compound B1 (140.27 g, 94.2%).

[0168] (ii) Compound B1 (140.27 g) was dissolved in 117.7 mL of ethanol, and 2 M sodium hydroxide aqueous solution (565 mL) was added. After reacting at 100 °C for 2 h, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound C1 (107.98 g, 90.6%).

[0169] (iii) Compound F (107.98 g) was dissolved in 341 mL of glacial acetic acid, and then... o Add sodium nitrite aqueous solution (2M, 427 mL) at C. The reaction proceeds at 0°C. o After 1 hour of treatment at C, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound F (93.11 g, 72.8%).

[0170] (iv) Compound F (93.11 g) was dispersed in dichloromethane (486 mL), and trifluoroacetic anhydride (169 mL) was added at 0 °C. The reaction was carried out at 45 °C. o After 2 hours at C, the product was poured into water to precipitate and filtered to obtain the bisysine monomer DSO1 (52.42 g, 62.3%). The DSO1... 1H NMR (400 MHz, DMSO-) d 6) Characterization results: δ ppm: 8.04 (d, 2H), 7.80 (s, 4H), 7.44 (d, 4H) Figure 1 ).

[0171] Preparation Example 1: Synthesis of Dibenzocyclooctadiyne

[0172] (i) Phthalate A1 (100 g), phthalaldehyde B1 (95 g) and potassium methoxide (13.45 g) were dissolved in 1200 mL of ethanol. After reacting at 25 °C for 2 h, the mixture was filtered to obtain compound C1 (142.32 g, 87.4%).

[0173] (ii) Compound C1 (142.32 g) was dissolved in a solution of trifluoroacetic acid (350 mL) and water (350 mL), and hydrochloric acid (350 mL) was added. After reacting at 80 °C for 12 h, the solution was diluted with water (700 mL), filtered, and dried at 80 °C for 12 h to obtain compound D1 (139.78 g, 85.5%).

[0174] (iii) Compound D1 (139.78 g) was dissolved in N-methylpyrrolidone (950 mL), and tetrakis(triphenylphosphine)palladium (27.62 g) and pyridine (2.83 g) were added. The mixture was reacted at 190 °C for 4 hours. The reaction solution was diluted with water (1000 mL), the pH was adjusted to 1 with concentrated hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic phases were combined and concentrated, and purified by rinsing a short silica gel column with toluene as the eluent to obtain compound E1 (78.20 g, 80.1%).

[0175] (iv) Compound E1 (78.20 g) was dissolved in chloroform (770 mL), and liquid bromine (128.8 g) was added. The mixture was refluxed under incandescent light for 4 hours. The reaction solution was cooled to room temperature, and saturated sodium sulfite aqueous solution was added. After stirring thoroughly, the mixture was allowed to stand and separated. The organic phase was collected, and the solvent was removed by rotary evaporation to obtain compound F1 (199.05 g, 99.9%).

[0176] (v) Compound F1 (199.05 g) was dissolved in dichloromethane (1530 mL), and sodium tert-butoxide (183.82 g) was added. The reaction was carried out at room temperature for 1 hour. The reaction was quenched with water, the organic phase was collected and concentrated, and purified by eluting with cyclohexane through a short silica gel column to give compound dibenzocyclooctadiyne (64.72 g, 84.5%). 11H NMR (400 MHz, CD3Cl) characterization results: δppm: 6.96-6.91 (dd, 4H), 6.76-6.71 (dd, 4H).

[0177] Preparation Example 2: Synthesis of Phenylenolnaphthylcyclooctadiyne

[0178] (i) 100 g of phthalonitrile A1, 124 g of 2,3-naphthalenedicarboxyl B2 and 20 g of sodium methoxide were dissolved in 1200 mL of ethanol. After reacting at 0 °C for 5 h, compound C2 (165.62 g, 85.0%) was obtained by filtration.

[0179] (ii) Compound C2 (165.62 g) was dissolved in a solution of propionic acid (360 mL) and water (360 mL), and concentrated sulfuric acid (360 mL) was added. After reacting at 150 °C for 2 h, the solution was diluted with water (1800 mL), filtered, and dried at 80 °C for 12 h to obtain compound D2 (160.42 g, 86.1%).

[0180] (iii) Compound D2 (160.42 g) was dissolved in xylene (950 mL), and cuprous bromide (7.76 g) and 1,10-o-phenoroline (12.29 g) were added. The mixture was reacted at 140 °C for 8 hours. The reaction solution was diluted with water (950 mL), and the pH was adjusted to 1 with concentrated hydrochloric acid. The mixture was extracted with ethyl acetate (3 × 950 mL), the organic phases were combined and concentrated, and purified by purifying with cyclohexane using a short silica gel column to obtain compound E2 (104.98 g, 88.1%).

[0181] (iv) Compound E2 (104.98 g) was dissolved in dichloromethane (830 mL), and liquid bromine (192.47 g) was added. The mixture was refluxed under incandescent light for 8 hours. Saturated sodium sulfite aqueous solution was added, and the mixture was stirred thoroughly and allowed to stand for separation. The organic phase was collected, and the solvent was removed by rotary evaporation to obtain compound F2 (234.22 g, 99.5%).

[0182] (v) Compound F2 (234.22 g) was dissolved in diethyl ether (1650 mL), and potassium hydroxide (161.14 g) was added. The reaction was carried out at 0 °C for 3 hours. The reaction was quenched with water, the organic phase was collected and concentrated, and purified by rinsing a short silica gel column with toluene as the eluent to give compound phenylnaphthylcyclooctadiyne (83.68 g, 81.4%). 1 ¹H NMR (400 MHz, CD₃Cl) characterization results: δ ppm: 6.93 6.95 (m, 2H), 7.05 7.06 (m, 2H), 7.25 7.27 (m, 2H), 7.36 7.38 (m, 2H), 7.53 7.55 (m, 2H).

[0183] Preparation Example 3: Synthesis of fluorophenyl o-dimethyl ether benzocyclooctadiyne

[0184] (i) 4,5-Dimethoxyphthalic acid acetonitrile A3 (100 g), 3-fluoro-phthalic anhydride B3 (73.87 g) and sodium tert-butoxide (24.74 g) were dissolved in 1000 mL of ethanol. After reacting at 25 °C for 2 h, the mixture was filtered to obtain compound C3 (134.78 g, 87.7%).

[0185] (ii) Compound C3 (134.78 g) was dissolved in a solution of trichloroacetic acid (270 mL) and water (270 mL), and concentrated hydrochloric acid (270 mL) was added. After reacting at 130 °C for 6 h, the solution was diluted with water (1620 mL), filtered, and dried at 80 °C for 12 h to obtain compound D3 (128.87 g, 85.8%).

[0186] (iii) Compound D3 (128.87 g) was dissolved in N,N-dimethylformamide (700 mL), and cuprous iodide (7.36 g) and N,N,N',N'-tetramethylethylenediamine (5.63 g) were added. The mixture was reacted at 170 °C for 4 hours. The reaction solution was diluted with water (700 mL), the pH was adjusted to 1 with concentrated hydrochloric acid, and the mixture was extracted with ethyl acetate (3 × 700 mL). The organic phases were combined and concentrated, and purified by rinsing a short silica gel column with n-hexane as the eluent to obtain compound E3 (82.91 g, 84.4%).

[0187] (iv) Compound E3 (82.91 g) was dissolved in carbon disulfide (600 mL), and liquid bromine (130.94 g) was added. The mixture was refluxed under incandescent light for 6 hours. Saturated sodium sulfite aqueous solution was added, and the mixture was stirred thoroughly and allowed to stand for separation. The organic phase was collected, and the solvent was removed by rotary evaporation to obtain compound F3 (175.51 g, 99.9%).

[0188] (v) Compound F3 (175.51 g) was dissolved in tetrahydrofuran (1200 mL), and potassium tert-butoxide (183.14 g) was added. The reaction was carried out at 10 °C for 2 hours. The reaction was quenched with water, extracted with diethyl ether, and the organic phase was collected and concentrated. The organic phase was purified by rinsing a short silica gel column with n-hexane as the eluent to give compound fluorophenyl dimethyl ether benzocyclooctadiyne (66.86 g, 81.9%). 1¹H NMR (400 MHz, CD₃Cl) characterization results: δ ppm: 3.79 (s, 6H), 6.32 (s, 1H), 6.33 (s, 1H), 6.39 (m, 1H); 6.54 (m, 1H); 6.58–6.61 (m, 1H).

[0189] Preparation Example 4 This preparation example has the same structural formula as the dibenzocyclooctadiyne compound prepared in Preparation Example 1. It was synthesized using a conventional four-step tandem reaction, and the overall synthetic route is as follows:

[0190] (i) At 0 °C, TMSCH2N2 (37.30 mL) was added dropwise to a mixed solution of 5-dibenzocycloheptenone (10 g) and boron trifluoride diethyl ether (9.50 mL) in dichloromethane (120 mL), and the reaction was carried out at 0 °C for 2 h. After the reaction was completed, 200 mL of water was added to the mixture, and the mixture was extracted with dichloromethane (3 g / mL). 200 mL). The organic phase was collected, the solvent was removed by vacuum distillation, and the crude product was finally purified by column chromatography. The eluent was PE / EA (v / v = 20 / 1), yielding compound B (5.66 g, 53.0%).

[0191] (ii) Compound B (5.66 g) was added to a solution of trifluoromethanesulfonic anhydride (14 mL) and N,N'-diisopropylethylamine (14 mL) in dichloromethane (160 mL), and the reaction was allowed to proceed at room temperature for 24 h. 200 mL of water was added to the reaction mixture, and the solution was extracted with DCM (3... 200 mL). The organic phase was collected, the solvent was removed by vacuum distillation, and the crude product was finally purified by column chromatography. The eluent was PE / EA (v / v = 30 / 1), yielding compound C (5.61 g, 62.0%).

[0192] (iii) Liquid bromine (1 mL) was added dropwise to a dichloromethane (90 mL) solution of compound C (5.61 g), and the reaction was allowed to proceed at room temperature for 24 h. Then, 100 mL of an aqueous solution of sodium thiosulfate (9.97 g) was added to the reaction mixture, and the mixture was extracted with dichloromethane (3... 100 mL). Collect the organic phase and remove the solvent by vacuum distillation to give compound D (7.72 g, 95.0%).

[0193] (iv) Potassium tert-butoxide (9.80 g) was added to a tetrahydrofuran (107 mL) solution of compound D (7.72 g), and the reaction was carried out at room temperature for 12 h. After the reaction was completed, 100 mL of water was added to the mixture, and the mixture was extracted with DCM (3... 100 mL). The organic phase was collected, the solvent was removed by vacuum distillation, and the crude product was finally purified by column chromatography. The eluent was petroleum ether to give dibenzocyclooctadiyne (2.42 g, 80.0%). 1 1H NMR (400 MHz, CD3Cl) characterization results: δ ppm: 6.96-6.91 (dd, 4H), 6.76-6.71 (dd, 4H).

[0194] Preparation Example 5-1 Synthesis of monosydinoketone compound SSO1

[0195] (i) Aniline (80 g), ethyl bromoacetate (102 mL) and sodium acetate (147.65 g) were dissolved in 500 mL of ethanol. After reflux for 4 h, deionized water was added and recrystallized to give compound D (140.27 g, yield >94%).

[0196] (ii) Compound E (140.27 g) was dissolved in 117.7 mL of ethanol and an aqueous sodium hydroxide solution (2 M, 564.5 mL) was added. After reflux for 2 h, the pH of the solution was adjusted to 1, and the mixture was filtered to obtain compound E (96.06 g, yield >81%).

[0197] (iii) Compound F (96.06 g) was dissolved in 303.7 mL of glacial acetic acid, and then... o Add sodium nitrite aqueous solution (2 M, 380 mL) at C. The reaction proceeds at 0°C. o After 1 hour of treatment at C, the pH of the solution was adjusted to 1, and the solution was filtered to obtain compound F (82.84 g, yield >71%).

[0198] (iv) Compound F (82.84 g) was dispersed in dichloromethane (432.2 mL), and trifluoroacetic anhydride (150.2 mL) was added at 0 °C. The reaction was carried out at 45 °C. o After 2 hours of precipitation at C, the product was poured into water (1 L) for precipitation and filtration to obtain the monosysyl ketone compound SSO1 monomer (43.7 g, yield >60%).

[0199] Preparation Example 5-2 Synthesis of monosydinoketone compound SSO2 The synthesis of SSO2 is similar to that of SSO1, except that aniline is replaced with p-methylaniline.

[0200]

[0201] Preparation Example 5-3 Synthesis of monosydinoketone compound SSO3 The synthesis of SSO3 is similar to that of SSO1, except that aniline is replaced with p-trifluoromethylaniline.

[0202]

[0203] Preparation Example 5-4 Synthesis of monosydinoketone compound SSO4 The synthesis of SSO4 is similar to that of SSO1, except that aniline is replaced with p-fluoroaniline.

[0204]

[0205] Preparation Example 5-5 Synthesis of monosydinoketone compound SSO5 The synthesis of SSO5 is similar to that of SSO1, except that aniline is replaced with cyclohexylamine.

[0206]

[0207] Preparation Examples 5-6: Synthesis of the monosydinoketone compound SSO6 The synthesis of SSO6 is similar to that of SSO1, except that aniline is replaced with p-hydroxyaniline.

[0208]

[0209] Application Example 1A Disylate DSO1 (30 mmol) and monosylate SSO1 (0.15 mmol) were dissolved in N-methylpyrrolidone at a concentration of 0.5 mol / L. Dibenzocyclooctadiyne BCODY (30.6 mmol) was slowly added at -10 °C, and the polymerization reaction was carried out at 25 °C for 2 hours. The polymerization solution was then precipitated in a methanol / tetrahydrofuran mixed solvent (1 / 1 by volume).

[0210] The synthesized polymer solid was vacuum dried at 100 °C and redissolved in N-methylpyrrolidone with a solid content of 15%. After filtration and degassing, the film was cast and coated to obtain a 25±3 μm film, named PBCO-1A. The infrared data of the film are shown in [reference needed]. Figure 16 The main performance characteristics are shown in Table 3.

[0211] Application Example 1B Dissylinone DSO1 (30 mmol) and monossylinone SSO1 (0.6 mmol) were dissolved in N-methylpyrrolidone at a concentration of 0.5 mol / L. Dibenzocyclooctadiyne BCODY (30.6 mmol) was slowly added at -10 °C, and the polymerization reaction was carried out at 25 °C for 2 hours. The polymerization solution was then precipitated in a methanol / tetrahydrofuran mixed solvent (1 / 1 by volume).

[0212] The synthesized polymer solid was vacuum dried at 100 °C and redissolved in N-methylpyrrolidone with a solid content of 15%. After filtration and degassing, the film was cast and coated to obtain a 25±3 μm film, named PBCO-1B. The infrared data of the film are shown in [reference needed]. Figure 16 The main performance characteristics are shown in Table 3.

[0213] Application Example 1C Dissylinone DSO1 (30 mmol) and monossylinone SSO1 (1.5 mmol) were dissolved in N-methylpyrrolidone at a concentration of 0.5 mol / L. Dibenzocyclooctadiyne BCODY (30.6 mmol) was slowly added at -10 °C, and the polymerization reaction was carried out at 25 °C for 2 hours. The polymerization solution was then precipitated in a methanol / tetrahydrofuran mixed solvent (1 / 1 by volume).

[0214] The synthesized polymer solid was vacuum dried at 100 °C and redissolved in N-methylpyrrolidone with a solid content of 15%. After filtration and degassing, the film was cast and coated to obtain a 25±3 μm film, named PBCO-1C. The infrared data of the film are shown in [reference needed]. Figure 16 The main performance characteristics are shown in Table 3.

[0215] Application Example 2: Aromatic Heterocyclic Polymer (PBCO-2) Disylate DSO2 (30 mmol) and monosylate SSO2 (0.15 mmol) were dissolved in N-ethylpyrrolidone at a concentration of 0.3 mol / L. Dibenzocyclooctadiyne BCODY (33 mmol) was slowly added at 10 °C, and the polymerization reaction was carried out at 20 °C for 12 hours. The polymerization solution was then precipitated in methanol.

[0216] The synthesized polymer solid was vacuum dried at 120 °C and redissolved in N-ethylpyrrolidone with a solid content of 20%. After filtration and degassing, the solution was cast and coated to obtain a 25±3 μm film, named PBCO-2. The infrared data of the film are shown in [reference needed]. Figure 17 The main performance characteristics are shown in Table 3.

[0217] Application Example 3: Aromatic Heterocyclic Polymer (PBCO-3) Disylate DSO3 (30 mmol) and monosylate SSO3 (0.15 mmol) were dissolved in N,N-dimethylacetamide at a concentration of 0.4 mol / L. Dibenzocyclooctadiyne BCODY (35 mmol) was slowly added at 0 °C, and the polymerization reaction was carried out at 15 °C for 6 hours. The polymerization solution was then precipitated, and the precipitate was a methanol / water mixture (volume ratio 8:1).

[0218] The synthesized polymer solid was vacuum dried at 80 °C and redissolved in N,N-dimethylacetamide with a solid content of 15%. After filtration and degassing, the film was cast and coated to obtain a 25±3 μm film, named PBCO-3. The infrared data of the film are shown in [reference needed]. Figure 18 The main performance characteristics are shown in Table 3.

[0219] Application Example 4: Aromatic Heterocyclic Polymer (PBCO-4) Dibenzo-Sydney ketone (DSO4) (30 mmol) and monobenzo-Sydney ketone (SSO4) (0.5 mmol) were dissolved in cyclopentanone at a concentration of 1.0 mol / L. Dibenzocyclooctadiyne (BCODY) (39 mmol) was slowly added at -10 °C, and the polymerization reaction was carried out at 40 °C for 4 hours. The polymerization solution was then precipitated, and the precipitate was methanol.

[0220] The synthesized polymer solid was vacuum dried at 120 °C and redissolved in cyclopentanone with a solid content of 15%. After filtration and degassing, the film was cast and coated to obtain a 25±3 μm film, named PBCO-4. The infrared data of the film are shown in [reference needed]. Figure 19 The main performance characteristics are shown in Table 3.

[0221] Application Example 5: Aromatic Heterocyclic Polymer (PBCO-5) Dissolve 30 mmol of disyringone DSO5 and 1 mmol of monosyringone SSO5 at a concentration of 1.5 mol / L in... γ In β-butyrolactone, dibenzocyclooctadiyne (BCODY) (40 mmol) was slowly added at 10 °C, and the polymerization reaction was carried out at 25 °C for 4 hours. The polymerization solution was then allowed to settle, and the settling liquid was a methanol / ethyl acetate mixture (volume ratio 2 / 1).

[0222] The synthesized polymer solid was vacuum dried at 80 °C and redissolved at a solid content of 15%. γ After filtration and degassing, a 25±3 μm film was prepared by casting and coating of β-butyrolactone, named PBCO-5. The infrared data of the film are shown in [reference needed]. Figure 20 The main performance characteristics are shown in Table 3.

[0223] Application Example 6: Aromatic Heterocyclic Polymer (PBCO-6) Disylate DSO6 (30 mmol) and monosylate SSO6 (4.5 mmol) were dissolved in N-methylpyrrolidone / dichlorobenzene (3:1 v / v) at a concentration of 1.2 mol / L. Dibenzocyclooctadiyne BCODY (45 mmol) was slowly added at -5 °C, and the polymerization reaction was carried out at 60 °C for 9 hours. The polymerization solution was then precipitated, and the precipitate was a methanol / ethanol mixture (1:1 v / v).

[0224] The synthesized polymer solid was vacuum dried at 100 °C and redissolved in N-methylpyrrolidone with a solid content of 15%. After filtration and degassing, the film was cast and coated to obtain a 25±3 μm film, named PBCO-6. The infrared data of the film are shown in [reference needed]. Figure 21 The main performance characteristics are shown in Table 3.

[0225] The overall yields of the examples and comparative examples are shown in Table 1.

[0226] Table 1 Overall yield of examples and comparative examples

[0227] As shown in Table 1, the overall yield of Examples 1-12 of the present invention is 64%-81% (specifically 64.2%-80.6%), while the overall yield of Comparative Example 1 is only 38.7%. This demonstrates that the overall yield of the three-step tandem reaction synthesis method of the present invention is higher than that of the existing four-step tandem reaction synthesis method. The yields of the preparation examples are shown in Table 2.

[0228] Table 2 Yield of the preparation example

[0229] As can be seen from Table 2, the yields of the first step reaction in Preparation Examples 1-3 of the present invention are 85.0%-87.7%, the yield of the second step reaction is 85.5%-86.1%, the yield of the third step reaction is 80.1%-88.1%, the yield of the fourth step reaction is 99.5%-99.9%, the yield of the fifth step reaction is 81.4%-84.5%, and the total yield is 50.5%-52.2%, while the total yield of Preparation Example 4 is only 25%. This proves that the total yield of the new synthesis method of the present invention is higher than the total yield of the existing four-step tandem reaction synthesis method.

[0230] Table 3. Main properties of aromatic heterocyclic polymers

[0231] Notes: Molecular weight was determined using gel permeation chromatography (GPC); solubility was evaluated by assessing the solubility of the polymer solid in the organic solvent DMAc / NMP, under the following conditions: 0.1 g sample was immersed at room temperature for 12 hours, and complete dissolution was recorded as ++; glass transition temperature was determined using dynamic thermomechanical analyzer (DMA), with the film sample under a nitrogen atmosphere and a heating rate of 20℃ / min; thermal decomposition temperature was determined using thermogravimetric analyzer (TGA), with a nitrogen atmosphere and a heating rate of 10℃ / min; tensile strength and elongation were tested using a universal tensile testing machine with a film sample thickness of 25±3 μm; transmittance was measured using a UV spectrophotometer with a film sample thickness of 10~15 μm; dielectric properties were measured using a dielectric spectrometer with a film sample thickness of 25±3 μm.

[0232] Table 3 lists the main performance data of the novel aromatic heterocyclic polymers synthesized in Application Examples 1-6. It can be seen that these novel aromatic heterocyclic polymers have very high molecular weights, for example, 85,000-321,000. Even with a low amount of monosydinoketone added, the number-average molecular weight of the polymer can still reach over 300,000. Comparing Examples 1A, 1B, and 1C, it can be seen that increasing the amount of monosydinoketone added can effectively adjust the molecular weight of the aromatic heterocyclic polymer, achieving efficient molecular weight design. These aromatic heterocyclic polymers all exhibit excellent solubility, dissolving in polar organic solvents at room temperature, thus enabling flexible processing.

[0233] Furthermore, these aromatic heterocyclic polymers exhibit high heat resistance, with glass transition temperatures and thermal decomposition temperatures reaching over 490°C and 540°C, respectively. Specifically, the aromatic heterocyclic polymers of this invention have a glass transition temperature of 442-495°C and a thermal decomposition temperature of 532-551°C.

[0234] Meanwhile, the aromatic heterocyclic polymers of the present invention also possess excellent mechanical properties. The tensile strength of the prepared film samples is all above 100 MPa, for example, 101-121 MPa; the films have high elongation at break, for example, 42%-77%, exhibiting good flexibility. In addition, these aromatic heterocyclic polymer films have excellent optical transparency in the visible light region, with a transmittance of above 80%, for example, 81.8%-88.7%, and a low dielectric constant (2.76-3.3) over a wide frequency range of megahertz.

[0235] The above results indicate that this type of novel aromatic heterocyclic polymer has a rich variety of structural designs and flexible performance adjustment. It has outstanding heat resistance, mechanical, optical, dielectric and processability properties. The material processing covers product forms such as thin films, resins and slurries. As a high-temperature resin, dielectric and substrate material, it has broad application prospects in the fields of electronics, microelectronics, energy, display, aviation and aerospace.

[0236] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a bis-sydnonyl end group compound, characterized by, The preparation method synthesizes the bis-Sydney ketone terminal compound through a three-step organic reaction, including the following steps: Step 1: Dissolve the primary amino compound, secondary amination reagent and base in a solvent to undergo secondary amination reaction, and recrystallize to obtain the i-th intermediate; Step 2: Dissolve the i-th intermediate, add a hydrolysis reagent to initiate a hydrolysis reaction, adjust the solution to be acidic, filter, and obtain the ii-th intermediate; Step 3: Dissolve intermediate ii, add nitrosating agent to induce nitrosation, add dehydrating agent to the reaction system to induce cyclization, and then post-process to obtain bis-Sydney ketone end-group compound.

2. The production method according to claim 1, characterized by, The molar ratio of the secondary amination reagent to the diprimary amino compound is (2.00~3.00):

1.

3. The production method according to claim 1 or 2, characterized by, In step 1, the structure of the diprimary amino compound is shown in formula A below: Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R includes at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

4. The method of claim 1, wherein, Secondary amination reagents include at least one of ethyl bromoacetate, ethyl chloroacetate, tert-butyl bromoacetate, tert-butyl chloroacetate, and methyl bromoacetate.

5. The preparation method according to claim 1, characterized in that, The secondary amination reaction temperature is 70~80℃, and the reaction time is 3-6h.

6. The method of claim 1, wherein, In step 2, the hydrolysis reaction temperature is 70~100℃ and the reaction time is 2-6h.

7. The preparation method according to claim 1, characterized in that, In step 2, the pH of the adjusted solution is 0.5-3.

8. The method of any one of claims 4-7, wherein, In step 3, the nitrification reaction is carried out at room temperature for 1-2 hours.

9. A bis-sydnonyl end group compound characterized by, The material is prepared by the preparation method according to any one of claims 1-8, and its structure is shown in the following formula DSO: Wherein, R includes at least one of aromatic, aliphatic, alicyclic, semi-aromatic, spirocyclic, and heterocyclic structures, and R includes at least one of ether bond, thioether bond, carbonyl group, carbonate group, amide bond, and fluorine element.

10. The application of the bisysine ketone end-group compound prepared by any one of claims 1-8 or the bisysine ketone end-group compound of claim 9 in the preparation of novel aromatic heterocyclic polymers.

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