Preparation method and application of primatone derivative and polymer thereof

Abstract

The invention belongs to the technical field of compound preparation, and particularly relates to a preparation method and application of a primatone derivative and a polymer thereof. The civet ketone derivative takes civet ketone as a core skeleton, and the macrocyclic structure of the civet ketone is subjected to controllable functional modification, so that the civet ketone derivative has good chemical stability and capability of further participating in chemical reaction. The primatone has a unique macrocyclic configuration and modifiable sites, and the derivative of the primatone can obtain new chemical properties and application potential on the basis of maintaining parent structure characteristics. The preparation method of the civet ketone derivative is easy and convenient to operate and mild in condition, and regulation and functionalization of the civet ketone structure can be efficiently achieved. The obtained civet ketone derivative can be applied to the preparation process of a polymer, and provides a new technical approach for the construction of a functional polymer by reacting with related components of a polymerization system to introduce a specific structural unit or improve the performance of a material.

Description

Technical Field

[0001] This invention belongs to the field of compound preparation technology, specifically relating to a series of civetone derivatives and their polymers, and their preparation methods and applications. Background Technology

[0002] Polymer materials are widely used in coatings, adhesives, elastomers, medical materials, and fine chemicals. With the development of novel functional materials, higher demands are being placed on the performance and structure of polymers, particularly in the precise control of molecular structure, the introduction of specific structural units, and the controllability of the polymerization process. In recent years, small organic molecule derivatives with designable molecular structures have gradually become important tools for achieving polymer structure control. By modifying their structures, materials with specific reactivity or functional properties can be obtained.

[0003] Civetones are a class of natural products with unique macrocyclic skeletons containing multiple modifiable sites, exhibiting good chemical reactivity and functionalization potential (Russ. Chem. Rev., 2020, 89, 469-490). By introducing different functional groups, civetone derivatives can significantly expand their chemical properties and applications, showing potential value in medicinal chemistry, materials science, and fine chemicals (Angew. Chem. Int. Ed. 2021, 133, 19837-19842). However, existing methods for preparing civetone derivatives are relatively limited, with some routes being cumbersome, lacking selectivity, or failing to achieve structural diversification, thus restricting their further development and application in the field of polymer materials.

[0004] With the increasing demand for green, efficient, and structurally controllable polymerization methods, the development of novel organic molecules that can serve as structural units or regulatory elements in polymerization systems is particularly important. The introduction of civetone derivatives into polymer structures holds promise for endowing materials with new physicochemical properties and providing new pathways for the design of functionalized polymers (Adv. Synth. Catal. 2002, 344, 507-510). However, currently available technologies lack systems for the efficient preparation of civetone derivatives, and no effective application techniques for their use in polymer synthesis have been identified.

[0005] Therefore, there is an urgent need to provide a controllable preparation method for civetone derivatives and to further explore their application in polymer synthesis, so as to expand the utilization of civetone structures and meet the needs of the polymer materials field for novel structural units and functionalization strategies. Summary of the Invention

[0006] To address the limitations of existing civetone derivatives in terms of structural modification, complex preparation steps, and insufficient application in polymer materials, the primary objective of this invention is to provide a class of structurally controllable civetone derivatives. Civetone molecules possess a unique macrocyclic skeleton structure and contain multiple chemically modifiable reaction sites. By rationally introducing functional groups, their molecular design space and chemical application potential can be significantly expanded, thereby laying the foundation for constructing novel functional materials.

[0007] Another objective of this invention is to provide a method for preparing the above-mentioned civetone derivatives. This method enables efficient and controllable functionalization of the civetone structure, and the resulting derivatives possess good chemical stability and characteristic groups that can be further reacted, effectively overcoming the problems of cumbersome steps, limited product types, and insufficient selectivity in traditional preparation methods.

[0008] Another object of this invention is to provide applications for the aforementioned civetone derivatives. The civetone derivatives described in this invention can be applied to polymer synthesis: by introducing civetone derivatives into polymer systems, they can participate in the polymerization process as structural units or functional groups, thereby controlling the composition, structure, or properties of the polymer and endowing the material with specific functional properties. The civetone derivatives constructed in this invention, and their application systems, expand the use of natural product structures in the polymer field, providing a new technical direction for the design and preparation of functionalized, high-performance polymer materials.

[0009] The present invention also provides civetone derivative polymers.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] The civetone derivatives provided by this invention can be mainly classified into ten main structures, including the following structures:

[0012]

[0013] In structural formulas LMT-A to LMT-J: R1 is a hydrogen atom, a sulfonyl group, or a substituted or unsubstituted C1-C50 alkyl or aryl group; R2 is a hydrogen atom, a cyclopropene cation, or a substituted or unsubstituted C1-C50 alkyl or aryl group; R3 is a hydrogen atom, a carbonyl group, an aldehyde group, an alkenyl ether, or an azide group; R4 and R5 are substituted or unsubstituted C1-C50 alkyl chains containing heteroatoms. It is a nitrogen-containing heterocycle.

[0014] Preferably, the sulfonyl group in R1 is an aliphatic sulfonyl group or an aromatic sulfonyl group; when R1 is a substituted C1-C50 alkyl or aryl group, R1 contains one or more of C, N, O, P, Si, and S atoms; when R2 is a substituted C1-C50 alkyl or aryl group, R2 contains one or more of C, N, O, P, Si, and S atoms; R3 is a hydrogen atom, carbonyl group, aldehyde group, alkenyl ether, or azide group; when R4 and R5 are substituted or unsubstituted C1-C50 alkyl chains containing heteroatoms, R4 and R5 contain one or more of N, O, P, Si, and S atoms, wherein R4 and R5 are covalently cyclic or non-cyclic.

[0015] Preferably, the substituent R1 group is selected from the following structures:

[0016]

[0017] Where n and m are integers from 1 to 50.

[0018] The R2 group is selected from the following structures:

[0019]

[0020] Wherein, n and m are integers from 1 to 50; X is a counterion, specifically one or more of the following: fluoride ion, chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hexafluorophosphate ion, carboxylate ion, lithium tetra(pentafluorophenyl)borate anion, nickel tetracarbonyl anion, carbonate ion, hypochlorite ion, phosphate ion, and phenoxy ion.

[0021] The R4 and R5 groups are selected from the following structures:

[0022]

[0023] Where n is an integer from 1 to 50.

[0024] Preferably, the nitrogen-containing heterocycle is selected from the following structures:

[0025]

[0026] The following structural formulas are some examples of the civetone derivatives described in this invention:

[0027]

[0028] This invention also provides synthetic steps for civetone derivatives with chemical structures LMT-A to LMT-E, as follows:

[0029] (1) Dissolve civetone LMT-0 in an organic solvent, then add sodium borohydride to react, and after the reaction is complete, civetone derivative LMT-1 is obtained;

[0030] (2) The civet derivative LMT-1 was dissolved in an organic solvent, and a base and 4-dimethylaminopyridine were added. Then, sulfonyl chloride was added to react. After the reaction was completed, the civet derivative was obtained.

[0031] When p-toluenesulfonyl chloride is added, the civetone derivative LMT-2-TS is prepared:

[0032]

[0033] (3) Dissolve civet derivative LMT-2 in an organic solvent, then add sodium azide to react, and after the reaction is complete, civet derivative LMT-3 is obtained;

[0034] (4) Dissolve civet derivative LMT-3 in an organic solvent, then add lithium aluminum hydride dropwise to react, and after the reaction is complete, civet derivative LMT-4 is obtained.

[0035] (5) Dissolve the civet derivative LMT-4 in an organic solvent, then add an acid anhydride and a base, or a halocyclopropene cation and a base to react, and the civet derivative is obtained after the reaction is completed.

[0036] (6) Dissolve civetone in an organic solvent, then add Pd / C, and after the reaction is complete, obtain civetone derivative LMT-0-R;

[0037] (7) Dissolve the civet derivative LMT-0-R in an organic solvent, then add sodium borohydride to react, and after the reaction is complete, the civet derivative LMT-1-R is obtained;

[0038] (8) Dissolve the civet derivative LMT-1-R in an organic solvent, add phosphorus oxychloride dropwise to react, and obtain the civet derivative LMT-R after the reaction is complete;

[0039] (9) Dissolve civetone in an organic solvent, add diol or alkylol, then add p-toluenesulfonic acid and triethyl orthoformate. After the reaction is complete, civetone derivative is obtained.

[0040] (10) Dissolve civetone in an organic solvent and add it to a phosphorus ylide solution. After the reaction is complete, the civetone derivative LMT-S-2 is obtained.

[0041] (11) Dissolve civet derivative LMT-S-2 in an organic solvent, add hydrochloric acid aqueous solution dropwise, and obtain civet derivative LMT-S-3 after the reaction is completed.

[0042] More preferably, in step (5),

[0043] When 1,8-naphthalenedicarboxylic anhydride is added, the chemical structure of the civetone derivative LMT-NI prepared is as follows:

[0044] When perylene-3,4-dicarboxylic anhydride is added, the chemical structure of the civetone derivative LMT-PMI prepared is as follows:

[0045] When benzo[a]perylene dicarboxylic anhydride is added, the chemical structure of the civetone derivative LMT-BPI prepared is as follows:

[0046] When a chlorocyclopropene cation is added, the chemical structure of the resulting civetone derivative LMT-TAC is as follows:

[0047] More preferably, in step (9), when ethylene glycol is added to the reaction, the chemical structure of the civetone derivative LMT-S-1 obtained is as follows:

[0048]

[0049] More preferably, the preparation method of the civetone derivative specifically includes the following steps:

[0050] (a) Civetone (LMT-0) was dissolved in an organic solvent (e.g., methanol), and sodium borohydride was slowly added at 0°C (the molar ratio of LMT-0 to sodium borohydride was 1:1 to 1:n, where n is greater than 1), followed by reaction at room temperature. After the reaction was complete, water was slowly added to the reaction solution at 0°C, and the reaction solution was then extracted with ethyl acetate, dried under vacuum, and concentrated to obtain the civetone derivative LMT-1.

[0051] (b) The civetone derivative LMT-1 (1.0 equiv) was dissolved in an organic solvent (e.g., dichloromethane), followed by the addition of a base (e.g., triethylamine) (1-50 equiv) and 4-dimethylaminopyridine (DMAP) (1-50 equiv) under an inert atmosphere, and the reaction mixture was placed in an ice-water bath. p-Toluenesulfonyl chloride (LMT-1 to p-toluenesulfonyl chloride in a molar ratio of 1:1 to 1:n, where n is greater than 1) was dissolved in an organic solvent (e.g., dichloromethane) and added dropwise to the above reaction mixture, and the reaction was carried out overnight at room temperature. After the reaction was completed, column chromatography was used to separate the civetone derivative LMT-2-TS.

[0052] (c) The civetone derivative LMT-2 was dissolved in an organic solvent (e.g., acetonitrile), and then sodium azide (the molar ratio of LMT-2 to sodium azide was 1:4–1:n, where n was greater than 4) was added under an inert atmosphere and refluxed overnight. After the reaction was complete, water was slowly added, and the mixture was extracted with dichloromethane. The organic phase was concentrated under reduced pressure and separated by column chromatography to obtain the civetone derivative LMT-3.

[0053] (d) The civetone derivative LMT-3 was dissolved in an organic solvent (e.g., tetrahydrofuran), and then lithium aluminum hydride (LMT-3 to lithium aluminum hydride molar ratio of 1:2-1:n, where n is greater than 2) was slowly added dropwise under an inert gas atmosphere, and the reaction was carried out overnight at room temperature. After the reaction was completed, a large amount of water was slowly added in an ice-water bath, and the mixture was extracted with ethyl acetate. The organic phase was concentrated under reduced pressure and separated by column chromatography to obtain the civetone derivative LMT-4.

[0054] (e) The civetone derivative LMT-4 was dissolved in an organic solvent (e.g., N,N-dimethylformamide) under an inert atmosphere, followed by the addition of 1,8-naphthalenedicarboxylic anhydride (the molar ratio of LMT-4 to 1,8-naphthalenedicarboxylic anhydride was 1.5:1 to 1.5:n, where n is less than 1) and N,N-diisopropylethylamine (DIPEA) (the molar ratio of DIPEA to LMT-4 was 1:1 to n:1, where n is greater than 1). The reaction was carried out overnight at 80°C. After the reaction was complete, the mixture was extracted with ethyl acetate, the organic phase was collected, concentrated under reduced pressure, and separated by column chromatography to obtain the civetone derivative LMI-NI.

[0055] (f) The civetone derivative LMT-4 was dissolved in an organic solvent (e.g., N,N-dimethylformamide) under an inert atmosphere, followed by the addition of perylene-3,4-dicarboxylic anhydride (the molar ratio of LMT-4 to perylene-3,4-dicarboxylic anhydride was 1.5:1 to 1.5:n, where n is less than 1) and N,N-diisopropylethylamine (DIPEA) (the molar ratio of DIPEA to LMT-4 was 1:1 to n:1, where n is greater than 1). The reaction was carried out overnight at 80°C. After the reaction was complete, the mixture was extracted, the organic phase was collected, concentrated under reduced pressure, and separated by column chromatography to obtain the civetone derivative LMI-PMI.

[0056] (g) The civetone derivative LMT-4 was dissolved in an organic solvent (e.g., N,N-dimethylformamide) under an inert atmosphere, followed by the addition of benzo[a]perylene dicarboxylic anhydride (the ratio of LMT-4 to benzo[a]perylene dicarboxylic anhydride was 1.5:1 to 1.5:n, where the ratio was less than 1) and N,N-diisopropylethylamine (DIPEA) (the molar ratio of DIPEA to LMT-4 was 1:1 to n:1, where n was greater than 1). The reaction was carried out overnight at 80°C. After the reaction was complete, the mixture was extracted, the organic phase was collected, concentrated under reduced pressure, and separated by column chromatography to obtain the civetone derivative LMI-BPI.

[0057] (h) The civetone derivative LMT-4 was dissolved in an organic solvent (e.g., N,N-dimethylformamide) under a nitrogen atmosphere, followed by the addition of chlorocyclopropene cations (the molar ratio of LMT-4 to chlorocyclopropene cations was 1.5:1 to 1.5:n, where n is less than 1) and N,N-diisopropylethylamine (DIPEA) (the molar ratio of DIPEA to LMT-4 was 1:1 to n:1, where n is greater than 1). The reaction was carried out overnight at 80°C. After the reaction was completed, the civetone derivative LMT-TAC was obtained by column chromatography.

[0058] (i) LMT-0 was dissolved in an organic solvent (e.g., ethyl acetate), and excess palladium on carbon was added. The reaction was carried out at room temperature under a hydrogen atmosphere until complete. The mixture was filtered and concentrated under vacuum to obtain the civetone derivative LMT-0-R.

[0059] (j) LMT-0-R was dissolved in an organic solvent (e.g., dichloromethane), and sodium borohydride was added (the molar ratio of LMT-0-R to sodium borohydride was 1:4-1:n, where n was greater than 4), followed by reaction at room temperature. After the reaction was complete, the mixture was extracted, dried under vacuum, and concentrated to obtain the civetone derivative LMT-1-R.

[0060] (k) At low temperature, phosphorus oxychloride (molar ratio of phosphorus oxychloride to LMT-1-R of 26:1-n:1, where n is greater than 26) was added dropwise to a mixed solution of LMT-1-R and dry pyridine (7-10 mL / 1 mmol LMT-1-R). After reacting for two hours, the mixture was allowed to react at room temperature for 24-72 h. After the reaction was complete, the mixture was adjusted to neutral, extracted, and the organic phase was collected, concentrated under reduced pressure, and separated by column chromatography to obtain the civetone derivative LMT-R.

[0061] (l) Compound LMT-0 was dissolved in an organic solvent (ultra-dry N,N-dimethylformamide). Ethylene glycol (molar ratio of ethylene glycol to LMT-0 was 1:4.4-1:n, where n was greater than 4.4) was slowly added at room temperature, and the mixture was stirred thoroughly. Then, p-toluenesulfonic acid (molar ratio of p-toluenesulfonic acid to LMT-0 was 0.2:1-n:1, where n was greater than 0.2) and triethyl orthoformate (molar ratio of triethyl orthoformate to LMT-0 was 3.6:1-n:1, where n was greater than 3.6) were added, and the reaction was carried out at 60°C. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The solution was then dried under vacuum and concentrated, and purified by column chromatography to obtain the civetone derivative LMT-S-1.

[0062] (m) Compound LMT-0 (0.6 equiv) (the molar ratio of LMT-0 to phosphorus ylide was 0.6:1-n:1, where n is less than 1) was dissolved in an organic solvent (ultra-dry tetrahydrofuran). The solution of phosphorus ylide was added to the solution in an ice-water bath, and the temperature was slowly raised to 40°C for 12 h. After the reaction was complete, water was added to the reaction solution at room temperature, followed by extraction with ethyl acetate, vacuum drying and concentration, and purification by column chromatography to obtain the civetone derivative LMT-S-2.

[0063] (n) Compound LMT-S-2 was dissolved in a small amount of organic solvent (ethyl acetate), and 10 wt% hydrochloric acid aqueous solution was added to it at room temperature. The reaction was allowed to proceed for 5 h. After the reaction was completed, the mixture was extracted with ethyl acetate, concentrated under vacuum, and purified by column chromatography to obtain the civetone derivative LMT-S-3.

[0064] This invention also provides a class of civetone derivative polymers, which are obtained by ring-opening polymerization of the civetone derivatives obtained above. The general polymerization steps are as follows:

[0065] One or more of civetone LMT-0 or civetone derivatives LMT-A to LMT-E are dissolved in an organic solvent (e.g., dichloromethane), and a Grubbs's catalyst is added to carry out a polymerization reaction. After the polymerization reaction is completed, a civetone derivative polymer is obtained.

[0066] Preferably, the solvent Grubbs's catalyst is any one or a combination of two or more of the first-generation, second-generation, or third-generation catalysts.

[0067] For example, in some preferred embodiments, referring to the ring-opening polymerization method described above, at least one of civetone LMT-0, civetone derivative LMT-3, civetone derivative LMT-NI, civetone derivative LMT-PMI, civetone derivative LMT-BPI, and LMT-R is dissolved in an organic solvent, and Grubbs's catalyst is added. After polymerization, a civetone derivative polymer is obtained. The following are some examples of the operation:

[0068] (a) Civet LMT-0 was dissolved in dichloromethane, and Grubbs's catalyst was added. After polymerization, polymer Poly(LMT-0) was obtained.

[0069] The chemical structure of Poly(LMT-0) is as follows:

[0070] (b) The civet derivative LMT-3 was dissolved in dichloromethane, and Grubbs's catalyst was added. After polymerization, the polymer Poly(LMT-3) was obtained.

[0071] The chemical structure of Poly(LMT-3) is as follows:

[0072] (c) The civetone derivative LMT-NI was dissolved in dichloromethane, and Grubbs's catalyst was added. After polymerization, the polymer Poly(LMT-NI) was obtained.

[0073] The chemical structure of Poly(LMT-NI) is as follows:

[0074] (d) The civet derivative LMT-PMI was dissolved in dichloromethane, and Grubbs's catalyst was added. After polymerization, the polymer Poly(LMT-PMI) was obtained.

[0075] The structure of Poly(LMT-PMI) is as follows:

[0076] (e) The civet derivative LMT-BPI was dissolved in dichloromethane, and Grubbs's catalyst was added. After polymerization, the polymer Poly(LMT-BPI) was obtained.

[0077] The structure of Poly(LMT-BPI) is as follows:

[0078] (f) The civet derivatives LMT-PMI and LMT-R were dissolved in dichloromethane, and Grubbs's catalyst was added. After polymerization, the polymer Poly(LMT-PMI-co-LMT-R) was obtained.

[0079] The chemical structure of Poly(LMT-PMI-co-LMT-R) is as follows:

[0080]

[0081] The civetone derivatives and their polymers described in this invention can be applied to supramolecular self-assembly, small molecule modification, polymer synthesis, hydrogel preparation, and the preparation of optoelectronic and mechanical materials.

[0082] The beneficial effects of this invention are:

[0083] (1) Compared with the prior art, the present invention prepares civetone derivatives with tunable structures and specific functional groups by controllably functionalizing the macrocyclic skeleton of civetone. These civetone derivatives are applicable to a variety of polymer synthesis systems and can participate in the construction of polymers as structural units or functional modules, thereby realizing the regulation of material composition or properties and expanding the application potential of civetone in the field of polymer materials.

[0084] (2) The preparation method of this invention is simple and efficient, and the obtained civetone derivatives are easy to introduce into different polymerization systems, providing new ideas for the design of various functionalized polymer materials. These civetone derivatives have good application prospects and can be further applied to more polymerization reactions and material development scenarios.

[0085] (3) The civetone derivative polymer of the present invention exhibits significantly improved thermal stability, making it suitable for high-temperature processing and functional material applications. Furthermore, the civetone derivative polymer of the present invention possesses stable and repeatable non-covalent interactions between molecules, enabling the system to construct a continuous nanoscale structural framework. The nanofiber network not only facilitates the formation of stable film morphologies but also provides structural advantages for mechanical reinforcement, ion / electron transport, and the construction of functional interfaces, giving the material potential advantages in applications such as functional films, conductive / ion transport materials, and biological or flexible devices. Attached Figure Description

[0086] Figure 1 The image shows the hydrogen nuclear magnetic resonance spectrum of LMT-1 prepared in Example 1 of this invention.

[0087] Figure 2 This is the carbon NMR spectrum of LMT-1 prepared in Example 1 of this invention.

[0088] Figure 3 The image shows the hydrogen nuclear magnetic resonance spectrum of LMT-2-TS prepared in Example 2 of this invention.

[0089] Figure 4 The image shows the carbon NMR spectrum of LMT-2-TS prepared in Example 2 of this invention.

[0090] Figure 5 The image shows the hydrogen nuclear magnetic resonance spectrum of LMT-3 prepared in Example 3 of this invention.

[0091] Figure 6 This is the carbon NMR spectrum of LMT-3 prepared in Example 3 of the present invention.

[0092] Figure 7 The image shows the hydrogen nuclear magnetic resonance spectrum of LMT-4 prepared in Example 4 of this invention.

[0093] Figure 8 This is the carbon NMR spectrum of LMT-4 prepared in Example 4 of this invention.

[0094] Figure 9 Thermogravimetric analysis diagrams of LMT-0 and Poly(LMT-0).

[0095] Figure 10 Thermogravimetric analysis diagrams of LMT-3 and Poly(LMT-3).

[0096] Figure 11 Thermogravimetric analysis (TGA) plots for LMT-PMI and Poly (LMT-PMI).

[0097] Figure 12 Image of an atomic force microscope (AFM) image of a Poly(LMT-PMI) self-assembled structure.

[0098] Figure 13 This is an atomic force microscope (AFM) image of Poly(LMT-BPI) self-assembly. Detailed Implementation

[0099] The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of protection of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the test methods in the following embodiments are conventional methods.

[0100] Example 1: Preparation of LMT-1

[0101] The reaction pathway is as follows:

[0102]

[0103] Compound LMT-0 (2.0 mmol, 1.0 equiv) was dissolved in methanol, and sodium borohydride (8.0 mmol, 4.0 equiv) was slowly added at 0 °C, followed by reaction at room temperature. After the reaction was complete, the reaction mixture was placed in an ice-water bath, and water was slowly added to the reaction solution. The reaction solution was then extracted with ethyl acetate, and the organic phase was collected, dried under vacuum, and concentrated to give a colorless liquid. Finally, the liquid was dried under vacuum for 12 h to give a colorless liquid LMT-1 (yield: 92%).

[0104] The LMT-1 proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ5.50-5.16(m,2H),3.80-3.57(m,1H),2.17-1.84(m,4H),1.68-1.17(m,24H).

[0105] The LMT-1 carbon NMR spectrum characterization is as follows: 13 C NMR (125MHz, CDCl3) δ130.24,70.50,35.69,29.11,28.29,28.03,27.94,26.86,23.55.

[0106] Example 2: Preparation of LMT-2-TS

[0107] The reaction pathway is as follows:

[0108]

[0109] Compound LMT-1 (2.0 mmol, 1.0 equiv) was dissolved in dichloromethane, followed by the addition of triethylamine (14.0 mmol, 7.0 equiv) and 4-dimethylaminopyridine (DMAP) (3.0 mmol, 1.5 equiv) under a nitrogen atmosphere. The reaction mixture was placed in an ice-water bath. p-Toluenesulfonyl chloride (4.0 mmol, 2.0 equiv) was dissolved in ultradry dichloromethane and slowly added dropwise to the above mixture. The reaction was then carried out overnight at room temperature under a nitrogen atmosphere. After the reaction was complete, water was added, and the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and the organic phase was concentrated under reduced pressure. The mixture was then separated by column chromatography (PE / EA: 9 / 1) to give a white solid LMT-2-TS (yield: 94%).

[0110] The LMT-2-TS proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ7.81-7.56 (m, 2H), 7.22 (d, J = 8.1Hz, 2H), 5.23 (t, J = 5.0Hz, 2H), 4. 51-4.38(m,1H),2.32(s,3H),2.04-1.80(m,4H),1.56-1.45(m,4H),1.33-1.00(m,20H).

[0111] The LMT-2-TS carbon NMR spectrum characterization is as follows: 13 C NMR (125MHz, CDCl3) δ130.24,70.50,35.69,29.11,28.29,28.03,27.94,26.86,23.55.

[0112] Example 3: Preparation of LMT-3

[0113] The reaction pathway is as follows:

[0114]

[0115] Compound LMT-2-TS (2.0 mmol, 1.0 equiv) was dissolved in ultra-dry acetonitrile, followed by the addition of sodium azide (8.0 mmol, 4.0 equiv) under a nitrogen atmosphere, and refluxed overnight. After the reaction was complete, water was slowly added, and the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and the organic phase was concentrated under reduced pressure and separated by column chromatography (PE) to give a colorless liquid LMT-3 (yield: 78%).

[0116] The LMT-3 proton NMR spectrum characterization is as follows: 1H NMR (500MHz, CDCl3) δ5.36-5.29(m,2H),3.39-3.34(m,1H),2.19-1.83(m,4H),1.57-1.53(m,4H),1.40-1.26(m,20H).

[0117] The LMT-3 carbon NMR spectrum characterization is as follows: 13 C NMR (125MHz, CDCl3) δ130.21,60.87,32.18,29.12,28.07,27.95,27.91,26.85,23.94.

[0118] Example 4: Preparation of LMT-4

[0119] The reaction pathway is as follows:

[0120]

[0121] Compound LMT-3 (2.0 mmol, 1.0 equiv) was dissolved in ultradry tetrahydrofuran, followed by the slow dropwise addition of lithium aluminum hydride (4.0 mmol, 2.0 equiv) under a nitrogen atmosphere, and the reaction was allowed to proceed overnight at room temperature. After the reaction was complete, a large amount of water was slowly added in an ice-water bath, followed by extraction with ethyl acetate, washing with saturated brine, drying over anhydrous sodium sulfate, and concentration of the organic phase under reduced pressure to give a colorless liquid, LMT-4 (yield: 87%).

[0122] The LMT-4 hydrogen nuclear magnetic resonance spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ5.536-5.29(m,2H),2.79-2.77(m,1H),2.08-1.97(m,4H),1.42-1.23(m,24H).

[0123] The LMT-4 carbon NMR spectrum characterization is as follows: 13 C NMR (125MHz, CDCl3) δ130.20,49.61,35.68,29.12,28.36,28.07,27.92,26.84,24.03.

[0124] Example 5: Preparation of LMT-NI

[0125] The reaction pathway is as follows:

[0126]

[0127] Compound LMT-4 (1.5 mmol, 1.5 equiv) was dissolved in N,N-dimethylformamide under a nitrogen atmosphere, followed by the addition of 1,8-naphthalenedicarboxylic anhydride (1.0 mmol, 1.0 equiv) and N,N-diisopropylethylamine (DIPEA) (1.5 mmol, 1.5 equiv). The reaction was carried out overnight at 80 °C. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added and stirred for 10 min. The mixture was extracted with ethyl acetate, and the organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by column chromatography (PE / EA: 10 / 1) to give a pale yellow solid LMT-NI (yield: 91%).

[0128] The LMT-NI proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ8.53(d,J=7.3Hz,2H),8.14(d,J=8.3Hz,2H),7.77-7.65(m,2H),5.37-5.31(m,2H),5.17- 5.11(m,1H),2.18-2.08(m,4H),2.05-2.00(m,2H),1.94-1.87(m,2H),1.47-1.37(m,10H),1.34-1.29(m,10H).

[0129] The LMT-NI carbon NMR spectrum characterization is as follows: 13 C NMR (125MHz, CDCl3) δ164.72,133.57,131.52,131.01,130.37,128.31,126.99,124.87,52.33,31.90,29.19,28.29,28.06,27.95,26.82,26.35.

[0130] Example 6: Preparation of LMT-PMI

[0131] The reaction pathway is as follows:

[0132]

[0133] Compound LMT-4 (1.5 mmol, 1.5 equiv) was dissolved in N,N-dimethylformamide under a nitrogen atmosphere, followed by the addition of perylene-3,4-dicarboxylic anhydride (1.0 mmol, 1.0 equiv) and N,N-diisopropylethylamine (DIPEA) (1.5 mmol, 1.5 equiv). The reaction was carried out overnight at 80 °C. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added and stirred for 10 min. The mixture was extracted with ethyl acetate, and the organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by column chromatography (PE / EA: 10 / 1) to give a red solid LMT-PMI (yield: 93%).

[0134] The LMT-PMI proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ8.57-8.48(m,2H),8.42-8.31(m,4H),7.88-7.85(s,2H),7.61-7. 58(m,2H),5.40-5.32(m,2H),5.20-5.15(m,1H),2.22-1.92(m,8H),1.43-1.30(m,20H).

[0135] The LMT-PMI carbon NMR spectroscopy characterization is as follows: 13 C NMR (125MHz, CDCl3) δ164.34,143.30,136.60,134.19,131.05,130.70,130.41,130.20,129.59,1 29.06,127.73,126.90,123.41,119.99,52.28,32.04,29.79,29.24,28.38,28.09,26.87,26.49.

[0136] Example 7: Preparation of LMT-BPI

[0137] The reaction pathway is as follows:

[0138]

[0139] Compound LMT-4 (1.5 mmol, 1.5 equiv) was dissolved in N,N-dimethylformamide under a nitrogen atmosphere, followed by the addition of benzo[a]perylene dicarboxylic anhydride (1.0 mmol, 1.0 equiv) and N,N-diisopropylethylamine (DIPEA) (1.5 mmol, 1.5 equiv). The reaction was carried out overnight at 80 °C. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added and stirred for 10 min. The mixture was extracted with ethyl acetate, and the organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by column chromatography (PE / EA: 10 / 1) to give a yellow solid LMT-BPI (yield: 87%).

[0140] The LMT-BPI proton NMR spectrum characterization is as follows: 1 H NMR(500MHz,THF-d8)δ9.24(d,J=9.0Hz,2H),9.17(d,J=7.8Hz,2H),8.27(d,J=11.6,8.3Hz,4H),8 .11(t,J=7.7Hz,2H),5.45-5.39(m,2H),4.47-4.42(m,1H),2.21-2.06(m,8H),1.57-1.40(m,20H).

[0141] The LMT-BPI carbon NMR spectroscopy characterization is as follows: 13 C NMR(125MHz,THF-d8)δ169.71,132.51,130.49,130.24,130.06,127.77,127.60,127.23,124. 87,124.38,123.91,122.78,122.12,49.05,30.93,28.95,28.08,27.80,27.36,26.48,25.40.

[0142] Example 8: Preparation of LMT-TAC

[0143] The reaction pathway is as follows:

[0144]

[0145] Compound LMT-4 (1.5 mmol, 1.5 equiv) was dissolved in N,N-dimethylformamide under a nitrogen atmosphere, followed by the addition of chlorocyclopropene cations (1.0 mmol, 1.0 equiv) and triethylamine (1.5 mmol, 1.5 equiv). The reaction was carried out overnight at 80 °C. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of water was added and stirred for 10 min. The mixture was extracted with ethyl acetate, and the organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by column chromatography (PE / EA: 10 / 1) to give a white solid LMT-TAC (yield: 75%).

[0146] The LMT-TAC proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ8.45 (d, J = 9.2Hz, 1H), 5.32-5.25 (m, 2H), 3.85-3.76 (m, 4H), 3.40-3.33 (m, 1H ),2.06-2.01(m,2H),1.96-1.90(m,2H),1.88-1.81(m,2H),1.77-1.70(m,2H),2.06-1.15(m,44H).

[0147] The LMT-TAC carbon NMR spectroscopy characterization is as follows: 13 C NMR (125MHz, CDCl3) δ130.24,116.97,113.07,57.65,50.64,33.90,29.09,28.18,28.14,27.97,26.69,24.98,22.21.

[0148] Example 9: Preparation of LMT-0-R

[0149] The reaction pathway is as follows:

[0150]

[0151] LMT-0 (1.0 mmol, 1.0 equiv) was dissolved in 5.0 mL of ethyl acetate, and excess palladium on carbon was added. The reaction was carried out at room temperature under a hydrogen atmosphere until complete. The mixture was filtered and concentrated under vacuum to obtain a colorless liquid, LMT-0-R (yield: 95%).

[0152] The LMT-0-R proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ2.39-2.37(m,4H),1.62-1.57(m,4H),1.30-1.24(m,24H).

[0153] The LMT-0-R carbon NMR spectrum characterization is as follows: 13C NMR (125MHz, CDCl3) δ212.68,42.47,28.26,27.89,27.64,27.31,27.22,26.94,23.83.

[0154] Example 10: Preparation of LMT-1-R

[0155] The reaction pathway is as follows:

[0156]

[0157] LMT-0-R (1.0 mmol, 1.0 equiv) was dissolved in methanol, and sodium borohydride (4.0 mmol, 4.0 equiv) was slowly added under an ice-water bath, followed by reaction at room temperature. After the reaction was complete, water was slowly added to the reaction solution at 0 °C, and the reaction solution was then extracted with ethyl acetate, dried under vacuum and concentrated to obtain a colorless liquid. Finally, the solution was dried under vacuum for 12 h to obtain a colorless liquid LMT-1-R (yield: 87%).

[0158] The LMT-1-R proton NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ3.71-3.66(m,1H),1.55-1.50(m,2H),1.48-1.41(m,2H),1.30-1.24(m,28H).

[0159] The LMT-1-R carbon NMR spectrum characterization is as follows: 13 C NMR (125MHz, CDCl3) δ70.94,35.78,27.89,27.69,27.61,27.55,27.45,27.41,23.76.

[0160] Example 11 Preparation of LMT-R

[0161] The reaction pathway is as follows:

[0162]

[0163] At 0–5 °C, phosphorus oxychloride (2.0 mmol, 26 equiv) was added dropwise to a mixed solution of LMT-1-R (1.0 mmol, 1 equiv) and dry pyridine (7.5 mL). After reacting for two hours, the mixture was allowed to react at room temperature for 24 hours. After the reaction was complete, the mixture was adjusted to neutral, extracted with ethyl acetate, and the organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by column chromatography (PE) to give a colorless liquid LMT-R (yield: 64%).

[0164] The LMT-R proton NMR spectrum characterization is as follows: 1H NMR (500MHz, CDCl3) δ5.38-5.31(m,2H),2.09-1.97(m,4H),1.87-1.68(m,12H),1.52-1.37(m,14H).

[0165] Example 12 Preparation of LMT-S-1

[0166] The reaction pathway is as follows:

[0167]

[0168] Compound LMT-0 (1.0 mmol, 1.0 equiv) was dissolved in ultradry N,N-dimethylformamide. Ethylene glycol (4.4 mmol, 4.4 equiv) was slowly added at room temperature, and the mixture was stirred thoroughly. Then, p-toluenesulfonic acid (0.2 mmol, 0.2 equiv) and triethyl orthoformate (3.6 mmol, 3.6 equiv) were added, and the reaction was carried out at 60 °C. After the reaction was complete, the mixture was cooled to room temperature, and water was slowly added to the reaction solution. The solution was then extracted with ethyl acetate, dried under vacuum, and concentrated to obtain a colorless liquid. The liquid was purified by column chromatography, and the product was dried under vacuum for 12 h to obtain the colorless liquid LMT-S-1 (yield: 95%).

[0169] The LMT-S-1 was characterized by its proton NMR spectrum as follows: 1 H NMR (500MHz, CDCl3) δ5.34-5.30(m,2H),3.91(s,4H),2.05(q,J=6.3Hz,4H),1.58-1.50(m,4H),1.40-1.28(m,20H).

[0170] Example 13 Preparation of LMT-S-2

[0171] The reaction pathway is as follows:

[0172]

[0173] Compound LMT-0 (0.6 mmol, 0.6 equiv) was dissolved in tetrahydrofuran. This solution was then added to a solution of phosphorus ylide (0.9 mmol, 1.5 equiv) in an ice-water bath. The mixture was slowly heated to 40 °C and reacted for 12 h. After the reaction was complete, water was slowly added to the reaction solution at room temperature, followed by extraction with ethyl acetate and concentration under vacuum. The product was purified by column chromatography and dried under vacuum for 12 h to give a colorless liquid, LMT-S-2 (yield: 100%).

[0174] The LMT-S-2 1H NMR spectrum characterization is as follows: 1H NMR (500MHz, CDCl3) δ5.73 (s, 1H), 5.37-5.25 (m, 2H), 3.51 (s, 3H), 2.08-2.01 (m, 6H), 1.87 (t, J = 7.0Hz, 2H), 1.34-1.20 (m, 20H).

[0175] Example 14 Preparation of LMT-S-3

[0176] The reaction pathway is as follows:

[0177]

[0178] Compound LMT-S-2 (1.0 mmol, 1.0 equiv) was dissolved in a small amount of ethyl acetate. A 10% aqueous hydrochloric acid solution was added at room temperature, and the reaction was allowed to proceed for 5 h. The mixture was extracted with ethyl acetate, concentrated under vacuum, purified by column chromatography, and the product was dried under vacuum for 12 h to give a colorless liquid, LMT-S-3 (yield: 80%).

[0179] The LMT-S-3 1H NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ9.60(t,J=2.7Hz,1H),5.33(d,J=5.0Hz,2H),2.26(d,J=6.2Hz ,1H),2.12-1.96(m,4H),1.73-1.57(m,2H),1.50-1.44(m,2H),1.41-1.22(m,20H).

[0180] The above embodiments yielded a series of civetone derivatives. To verify their applicability in polymer synthesis, the derivatives were used for homopolymerization and copolymerization reactions between different civetone derivatives.

[0181] Application Example 1: Preparation of Poly(LMT-0)

[0182] The aggregation path is as follows:

[0183]

[0184] In a glove box, compound LMT-0 (10.0 mmol, 50.0 equiv) was dissolved in 1400 μL of ultradry dichloromethane, and Grubbs's third-generation catalyst [G3] (0.2 mmol, 1.0 equiv) was dissolved in 200 μL of ultradry dichloromethane. These solutions were rapidly transferred to the LMT-0 mixture, and the reaction was allowed to proceed for 30 min. The sample was then removed, and a large amount of vinyl diethyl ether was added. The mixture was stirred for 30 min. After washing with ethyl acetate, methanol, and n-hexane, the sample was centrifuged several times and dried under vacuum to obtain a white solid, Poly(LMT-0) (yield: 95%).

[0185] The Poly(LMT-0) proton NMR spectroscopy characterization is as follows: 1 H NMR (500MHz, C2D2Cl4) δ4.69-4.67(m,2H),1.66(t,J=7.4Hz,4H),1.37-1.21(m,4H),0.85-0.79(m,4H),0.59(d,J=29.0Hz,16H).

[0186] Poly(LMT-0) carbon NMR characterization is as follows: 13 C NMR (125MHz, CDCl3) δ211.53,129.63,42.26,32.11,29.10,28.83,28.74,28.56,26.71,23.38.

[0187] Application Example 2: Preparation of Poly(LMT-3)

[0188] The aggregation path is as follows:

[0189]

[0190] In a glove box, compound LMT-3 (10.0 mmol, 50.0 equiv) was dissolved in 1400 μL of ultradry dichloromethane, and Grubbs's third-generation catalyst [G3] (0.2 mmol, 1.0 equiv) was dissolved in 200 μL of ultradry dichloromethane. The solutions were rapidly transferred to the LMT-3 mixture, and the reaction was allowed to proceed for 30 min. The sample was then removed, and a large amount of ethyl acetate was added and stirred for 30 min. The mixture was washed with ethyl acetate, methanol, and n-hexane, centrifuged multiple times, and dried under vacuum to obtain a white solid, Poly(LMT-3) (yield: 92%).

[0191] The Poly(LMT-3) hydrogen NMR spectrum characterization is as follows: 1 H NMR (500MHz, CDCl3) δ5.40-5.32(m,2H),3.23-3.18(m,1H),2.08-1.89(m,4H),1.60-1.53(m,4H),1.47(t,J=7.1Hz,4H),0.87-0.79(m,16H).

[0192] Application Example 3: Preparation of Poly(LMT-4)

[0193] The aggregation path is as follows:

[0194]

[0195] In a glove box, compound LMT-NI (40.0 mmol, 200.0 equiv) was dissolved in 1400 μL of ultradry dichloromethane, and Grubbs's third-generation catalyst [G3] (0.2 mmol, 1.0 equiv) was dissolved in 200 μL of ultradry dichloromethane. These solutions were then rapidly transferred to the LMT-NI mixture, and the reaction was allowed to proceed for 30 min. The sample was removed, and a large amount of ethyl acetate was added and stirred for 30 min. The mixture was then washed with ethyl acetate, methanol, and n-hexane, centrifuged multiple times, and dried under vacuum to obtain a pale yellow solid, Poly(LMT-NI) (yield: 90%).

[0196] The 1H NMR characterization of Poly(LMT-NI) is as follows: 1 H NMR(500MHz, CDCl3)δ8.56(d,J=19.3Hz,2H),8.20-8.15(m,2H),7.73(t,J=7.7Hz,2H),5.27 -5.22(m,2H),5.19-5.02(m,1H),2.36-2.14(m,2H),1.98-1.68(m,6H),1.33-1.18(m,20H).

[0197] Application Example 4: Preparation of Poly(LMT-PMI)

[0198] The aggregation path is as follows:

[0199]

[0200] In a glove box, compound LMT-PMI (40.0 mmol, 200.0 equiv) was dissolved in 1400 μL of ultradry dichloromethane, and Grubbs's third-generation catalyst [G3] (0.2 mmol, 1.0 equiv) was dissolved in 200 μL of ultradry dichloromethane. These solutions were then rapidly transferred to the LMT-PMI mixture, and the reaction was allowed to proceed for 30 min. The sample was removed, and a large amount of vinyl diethyl ether was added and stirred for 30 min. The mixture was then washed with ethyl acetate, methanol, and n-hexane, centrifuged multiple times, and dried under vacuum to obtain an orange solid, Poly(LMT-PMI) (yield: 85%).

[0201] The Poly(LMT-PMI) proton NMR spectroscopy characterization is as follows: 1 H NMR (500MHz, CDCl3) δ8.50-7.52(m,8H),5.34-5.24(m,2H),5.21-5.07(m,1H),2.00-1.77(m,4H),1.42-1.14(m,24H).

[0202] Application Example 5: Preparation of Poly(LMT-BPI)

[0203] The aggregation path is as follows:

[0204]

[0205] In a glove box, compound LMT-BPI (40.0 mmol, 200.0 equiv) was dissolved in 1400 μL of ultradry dichloromethane, and Grubbs's third-generation catalyst [G3] (0.2 mmol, 1.0 equiv) was dissolved in 200 μL of ultradry dichloromethane. These solutions were rapidly transferred to the LMT-BPI mixture, and the reaction was allowed to proceed for 30 min. The sample was then removed, and a large amount of vinyl diethyl ether was added and stirred for 30 min. The mixture was washed with ethyl acetate, methanol, and n-hexane, centrifuged multiple times, and dried under vacuum to obtain a yellow solid, Poly(LMT-BPI) (yield: 89%).

[0206] Poly(LMT-BPI) proton NMR spectroscopy characterization is as follows: 1 H NMR(500MHz,THF-d8)δ9.26-9.18(m,4H),8.32-8.25(m,4H),8.12(t,J=7.9Hz,2H) ,5.39(d,J=5.1Hz,2H),4.68-4.27(m,1H),2.23-2.00(m,8H),1.57-1.37(m,20H).

[0207] Application Example 6: Preparation of Poly(LMT-PMI-co-LMT-R)

[0208] The aggregation path is as follows:

[0209]

[0210] In a glove box, compounds LMT-PMI (10 mmol, 50.0 equiv) and LMT-R (10 mmol, 50.0 equiv) were dissolved in 1400 μL of ultradry dichloromethane, and Grubbs's third-generation catalyst [G3] (0.2 mmol, 1.0 equiv) was dissolved in 200 μL of ultradry dichloromethane. The solutions were rapidly transferred to the LMT-PMI and LMT-R mixture, and the reaction was allowed to proceed for 30 min. The sample was then removed, and a large amount of vinyl diethyl ether ester was added and stirred for 30 min. The mixture was washed with ethyl acetate, methanol, and n-hexane, centrifuged multiple times, and dried under vacuum to obtain a yellow solid, Poly(LMT-PMI-co-LMT-R) (yield: 78%).

[0211] Application Example 7: Thermogravimetric Analysis of LMT-0 and Poly(LMT-0)

[0212] Figure 9These are thermogravimetric analysis (TGA) graphs of LMT-0 and Poly(LMT-0). There is a fundamental difference in thermal stability between the monomer LMT-0 and the polymer Poly(LMT-0). The monomer LMT-0 begins to decompose at approximately 180℃, exhibiting typical characteristics of small-molecule thermal instability and difficulty to withstand higher temperatures. In contrast, the polymer Poly(LMT-0) shows a significantly increased decomposition temperature of 428℃, with a markedly delayed weight loss behavior, indicating that the polymeric backbone formed after polymerization significantly enhances the material's heat resistance. These results demonstrate that the polymerization process effectively improves the overall thermal stability of the system, transforming the material from a monomer with limited thermal stability into a polymeric system suitable for high-temperature environments and functional material applications.

[0213] Application Example 8: Thermogravimetric Analysis of LMT-3 and Poly(LMT-3)

[0214] Figure 10 These are thermogravimetric analysis (TGA) curves for LMT-3 and Poly(LMT-3). The TGA curves show a significant difference in thermal stability between the monomer LMT-3 and the polymer Poly(LMT-3). The monomer undergoes significant weight loss at approximately 320℃, and its decomposition process exhibits multi-stage characteristics, indicating that its small molecular structure is prone to volatilization or breakage during heating, resulting in low thermal stability. In contrast, the decomposition initiation temperature of Poly(LMT-3) is significantly higher at 418℃, and the weight loss process is delayed, indicating that the polymer backbone formed by polymerization effectively suppresses low-temperature thermal decomposition behavior. Simultaneously, the polymer retains a certain residual mass in the high-temperature region, demonstrating a more stable skeletal structure. Overall, polymerization significantly improves the thermal stability of the materials, making them more suitable for high-temperature processing and functional material applications.

[0215] Application Example 9: Thermogravimetric Analysis of LMT-PMI and Poly(LMT-PMI)

[0216] Figure 11These are thermogravimetric analysis (TGA) plots of LMT-PMI and Poly(LMT-PMI). The TGA results show a difference in thermal stability before and after polymerization. The monomer LMT-PMI begins to decompose significantly at approximately 322℃, exhibiting typical small-molecule characteristics, with a low thermal decomposition initiation temperature and rapid weight loss, indicating limited stability of its molecular backbone at high temperatures. In contrast, the polymer Poly(LMT-PMI) decomposes significantly at 389℃, with a significantly delayed weight loss initiation, indicating that polymerization effectively enhances the overall stability of the molecular structure. This improvement can be attributed to the covalent backbone structure formed after polymerization and the multi-point cooperative fracture characteristics, requiring higher energy input for thermal decomposition. Therefore, polymerization not only suppresses low-temperature thermal decomposition at the structural level but also enables the material to withstand higher temperature conditions, thus expanding its potential applications from monomeric molecular or intermediate systems to the field of high-temperature functional polymer materials.

[0217] Application Example 10: Assembly morphology of self-assembled supramolecular polymers of Poly (LMT-PMI) under atomic force microscopy

[0218] Atomic force microscope images ( Figure 12 This indicates that the supramolecular polymer can self-assemble into a continuous nanofiber structure, with the fibers interwoven to form a network morphology. This one-dimensional nanofiber characteristic suggests stable intermolecular forces, which is beneficial for constructing continuous transport channels or mechanical support structures, giving the material potential advantages in applications such as functional thin films, conductive / ion transport materials, and biological or flexible devices.

[0219] Application Example 11: Assembly morphology of self-assembled supramolecular polymers of Poly (LMT-BPI) under atomic force microscopy

[0220] The assembly morphology of the self-assembled supramolecular polymer of Poly(LMT-BPI) under atomic force microscopy is as follows: Figure 13 As shown in the AFM images, Poly(LMT-BPI) self-assembles on the substrate surface to form a continuous, flexible one-dimensional nanofiber structure. The fiber length reaches the micrometer scale and exhibits entanglement and networking characteristics. This morphology indicates the existence of stable and repeatable non-covalent interactions between polymer molecules, enabling the system to construct a continuous nanoscale structural framework. The nanofiber network not only facilitates the formation of stable film morphologies but also provides structural advantages for mechanical reinforcement, ion / electron transport, and the construction of functional interfaces, demonstrating the potential value of Poly(LMT-BPI) in functional materials and high-performance polymer applications.

[0221] Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention. This invention may also have other various embodiments. Without departing from the spirit and essence of this invention, those skilled in the art can make various corresponding changes and modifications according to this invention, but all such corresponding changes and modifications should fall within the protection scope of the appended claims.

Claims

1. A civetone-based civetone derivative, characterized in that, The chemical structural formula of the civetone derivative is shown below: In structural formulas LMT-A to LMT-J: R1 is a hydrogen atom, a sulfonyl group, or a substituted or unsubstituted C1-C50 alkyl or aryl group; R2 is a hydrogen atom, a cyclopropene cation, or a substituted or unsubstituted C1-C50 alkyl or aryl group; R3 is a hydrogen atom, a ketone group, an aldehyde group, an alkenyl ether, a carboxyl group, an ester group, a hydroxyalkyl group, or an azide group; R4 and R5 are substituted or unsubstituted C1-C50 alkyl chains containing heteroatoms. It is a nitrogen-containing heterocycle.

2. The civetone derivative according to claim 1, characterized in that, The sulfonyl group in R1 is an aliphatic sulfonyl group or an aromatic sulfonyl group; when R1 is a substituted C1-C50 alkyl or aryl group, R1 contains one or more of C, N, O, P, Si, and S atoms; when R2 is a substituted C1-C50 alkyl or aryl group, R2 contains one or more of C, N, O, P, Si, and S atoms; when R4 and R5 are substituted or unsubstituted C1-C50 alkyl chains containing heteroatoms, R4 and R5 contain one or more of N, O, P, Si, and S atoms, wherein R4 and R5 are covalently cyclic or acyclic.

3. The civetone derivative according to claim 1 or 2, characterized in that, The substituent R1 is selected from the following structures: Where n and m are integers from 1 to 50; The substituent R2 is selected from the following structures: Wherein, n and m are integers from 1 to 50; X is a counterion, specifically one or more of the following: fluoride ion, chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hexafluorophosphate ion, carboxylate ion, lithium tetra(pentafluorophenyl)borate anion, nickel tetracarbonyl anion, carbonate ion, hypochlorite ion, phosphate ion, and phenoxy ion. The substituents R4 and R5 are selected from the following structures: Where n is an integer from 1 to 50.

4. The civetone derivative according to claim 1 or 2, characterized in that, The It is a nitrogen-containing heterocycle, specifically selected from the following chemical structural formulas:

5. The civetone derivative according to claim 1 or 2, characterized in that, The structural formula of the civetone derivative is as follows:

6. The method for preparing the civetone derivative according to any one of claims 1-5, characterized in that, The synthetic steps for civetone derivatives with chemical structures LMT-A to LMT-E are as follows: (1) Dissolve civetone in an organic solvent, then add sodium borohydride to react, and after the reaction is complete, the civetone derivative LMT-1 is obtained; (2) Dissolve civet derivative LMT-1 in an organic solvent, add alkali and 4-dimethylaminopyridine, then add sulfonyl chloride to react, and after the reaction is complete, civet derivative LMT-2 is obtained. (3) Dissolve civet derivative LMT-2 in an organic solvent, then add sodium azide to react, and after the reaction is complete, civet derivative LMT-3 is obtained; The chemical structure of LMT-3 is as follows: (4) Dissolve civet derivative LMT-3 in an organic solvent, then add lithium aluminum hydride dropwise to react, and after the reaction is complete, civet derivative LMT-4 is obtained. The chemical structure of LMT-4 is as follows: (5) Dissolve the civet derivative LMT-4 in an organic solvent, then add an acid anhydride and a base, or a halocyclopropene cation and a base to react, and the civet derivative is obtained after the reaction is completed. (6) Dissolve civetone in an organic solvent, then add Pd / C, and after the reaction is complete, obtain civetone derivative LMT-0-R; The chemical structure of LMT-0-R is as follows: (7) Dissolve civet derivative LMT-0-R in an organic solvent, then add sodium borohydride to react, and after the reaction is complete, obtain civet derivative LMT-1-R; The chemical structure of LMT-1-R is as follows: (8) Dissolve the civet derivative LMT-1-R in an organic solvent, add phosphorus oxychloride dropwise to react, and obtain the civet derivative LMT-R after the reaction is complete; The chemical structure of LMT-R is as follows: (9) Dissolve civetone in an organic solvent, add diol or alkylol, then add p-toluenesulfonic acid and triethyl orthoformate. After the reaction is complete, civetone derivative is obtained. (10) Dissolve civetone in an organic solvent and add it to a phosphorus ylide solution. After the reaction is complete, the civetone derivative LMT-S-2 is obtained. The chemical structure of LMT-S-2 is as follows: (11) Dissolve civet derivative LMT-S-2 in an organic solvent, add hydrochloric acid aqueous solution dropwise, and obtain civet derivative LMT-S-3 after the reaction is complete; The chemical structure of LMT-S-3 is as follows:

7. The method for preparing the civetone derivative according to claim 6, characterized in that, The organic solvent is any one or a combination of two or more of N,N-dimethylformamide, tetrahydrofuran, acetonitrile, methanol, ethyl acetate, and dichloromethane; the base is any one or a combination of two or more of triethylamine, potassium carbonate, N,N-diisopropylethylamine, sodium carbonate, and pyridine.

8. A civetone derivative polymer, characterized in that, The polymer is prepared by dissolving one or more of civetone LMT-0 or civetone derivatives according to any one of claims 1-5 in an organic solvent, adding Grubbs's catalyst, and then carrying out a polymerization reaction. The solvent Grubbs's catalyst is any one or a combination of two or more of the first-generation, second-generation, or third-generation catalysts.

9. The civetone derivative polymer according to claim 8, characterized in that, The polymer structure of the civetone derivative is as follows:

10. The application of the civetone derivative according to any one of claims 1-5 and the civetone derivative polymer according to any one of claims 8-9, characterized in that, The civetone derivatives and their polymers are used in supramolecular self-assembly, small molecule modification, polymer synthesis, hydrogel preparation, and the preparation of optoelectronic or mechanical materials.

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