Triphenylamine monomers containing naphthofuran structure, polyamides thereof, and preparation methods and applications thereof

Abstract

Monomer containing naphthofuran and triphenylamine structure and polyamide and preparation method and application thereof. The present application relates to a monomer containing a mother nucleus and a triphenylamine group: N1, N1'-(dinaaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine) and a preparation method and application of a polyamide. The present application is to solve the problems of low solubility of polyamide materials in organic solvents, difficult film formation and single function. In the present application, the oxygen atom ring structure is introduced, the planarity and fluorescence intensity of the monomer are increased, the color changing ability and stability of the polymer are improved; the methoxy and triphenylamine are introduced, the solubility of the polymer is improved, the polymer is easily soluble in organic solvents, and the starting potential is reduced; the polymer has good electrochromic performance, low explosive detection limit and resistance memory storage performance, and solves the problem of single function. The present application is applied to the fields of electrochromic display, sensing, memory and photoelectric detection.

Description

Technical Field

[0001] This invention relates to triphenylamine polyamides containing naphthofuran, their preparation methods, and applications. Background Technology

[0002] Electrochromism refers to the reversible and continuous color change of certain optical properties of a material under the influence of an applied electric field. As a novel type of energy-saving material, electrochromic materials have shown broad application prospects due to their low energy consumption and controllable color, such as smart windows and information displays in energy-efficient buildings, self-dimming rearview mirrors in automobiles, electronic paper, military camouflage, and electrochromic electronic skin.

[0003] Triphenylamine derivatives, with their unique propeller-like structure, excellent electron-donating properties, and superior physical, photochemical, and electrochemical characteristics, are widely used as hole transport, memory devices, and electrochromic materials. Polymers containing triphenylamine not only possess excellent thermal stability and processability but also outstanding optoelectronic properties, making them a current research hotspot in optoelectronic materials. However, to meet the requirements of commercial applications, some key properties still need improvement, and multifunctional devices are required. Therefore, it is necessary to design new materials with multiple functions to meet future needs.

[0004] Aromatic polyamides possess several excellent properties, including stable thermal properties, oxidation resistance, high mechanical strength, and chemical corrosion resistance, leading to their wide application in civil engineering, transportation, national defense, aerospace, and electronics. However, the high benzene ring content in the polyamide molecular structure, the strong rigidity of the polyamide chain, and the intermolecular hydrogen bonding result in unsatisfactory solubility and processability of polyamide polymers, thus limiting their application range.

[0005] This invention introduces an oxygen atom ring structure into the polymer, which increases the planarity of the structure, conjugated conductivity, fluorescence intensity, color-changing ability of the polymer, and stability in use; the introduction of methoxy and triphenylamine improves the solubility of the polymer, making it more soluble in organic solvents, thereby improving its solubility and processability.

[0006] Compared with previously synthesized polyamides, the triphenylamine polyamide containing naphthofuran provided by this invention has multifunctional properties: it has excellent electrochromic properties in the 0-1.3V voltage range; low explosive detection limit; and rewritable and rereadable flash memory-type memristor performance with an on / off current ratio reaching 10. 3 The material of this invention possesses properties such as electrochromic display, photoelectric detection, and memory, making it multifunctional and applicable to various settings. Summary of the Invention

[0007] This invention addresses the problems of low solubility, poor processability, difficult device fabrication, and limited functionality of aromatic polyamides in organic solvents. It proposes a triphenylamine polyamide containing naphthofuran, its preparation method, and its applications. This results in a class of memristors exhibiting excellent electrochromic properties, low explosion detection limits, and stable performance, with practical applications in these three areas.

[0008] The triphenylamine polyamide containing naphthol in this invention is a polyamide synthesized from a diamine monomer containing a core and a triphenylamine structure and a diacid monomer (the diacid can be cyclohexanediol, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 4,4'-dicarboxydiphenyl ether, terephthalic acid, phthalic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl sulfone, etc.).

[0009] The structural formula of the triphenylamine polyamide P1 containing naphthofuran is as follows:

[0010]

[0011] In the formula, n is an integer from 3 to 20;

[0012] The structural formula of the triphenylamine polyamide P2 containing naphthofuran is as follows:

[0013]

[0014] In the formula, n is an integer from 3 to 20;

[0015] The structural formula of the triphenylamine polyamide P3 containing naphthofuran is as follows:

[0016]

[0017] In the formula, n is an integer from 3 to 20.

[0018] The structural formula of the triphenylamine polyamide P4 containing naphthofuran is as follows:

[0019]

[0020] In the formula, n is an integer from 3 to 20.

[0021] The method for preparing triphenylamine polyamide containing naphthofuran as described in claim 1 is characterized in that the preparation method comprises:

[0022] I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer:

[0023] ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine if the reaction was complete. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water, followed by filtration and rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, named M1.

[0024] The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1;

[0025] The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL.

[0026] The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0027] ② Add M1 and liquid bromine to a three-necked flask, incubate in chloroform solution on an ice bath for 2 hours, then move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow, and chloroform is used for extraction. An appropriate amount of anhydrous sodium sulfate is added to the organic layer for drying; then, the mixture is filtered and the crude product is obtained by rotary evaporation. Next, recrystallization is performed using chloroform, and the product is dried under vacuum to obtain a white solid product, named M2.

[0028] In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5;

[0029] In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL.

[0030] The temperature of the cold water mentioned in step 1② is 0℃;

[0031] The room temperature mentioned in step 1② is 25℃;

[0032] The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0033] ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6 ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporation of the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3.

[0034] The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2;

[0035] In step 1③, the molar ratio of M2 to potassium carbonate is 1:7;

[0036] The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1;

[0037] The molar ratio of M2 to copper powder mentioned in step 1③ is 1:7;

[0038] In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol;

[0039] The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol;

[0040] The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0041] Anhydrous ethanol, Pd / C, and M3 were added to a three-necked flask at room temperature. N2 was introduced into the flask, and hydrazine hydrate was added dropwise to the mixed solution in the flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, a saturated sodium chloride solution was added until no solid phase precipitated. The solid phase was filtered out and washed with water. Then, it was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4.

[0042] The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol;

[0043] In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol.

[0044] In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute.

[0045] The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol;

[0046] The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4);

[0047] The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C;

[0048] The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%.

[0049] The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0050] II. Preparation of triphenylamine polyamides containing naphthofuran:

[0051] M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol and acetone to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor.

[0052] The molar ratio of M4 to the diacid monomer in step two is 1:1;

[0053] The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0054] The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0055] The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0056] The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL;

[0057] In step two, the ratio of the volume of methanol added to the amount of M4 during the precipitation of solid is (200-250) mL: 1 mmol.

[0058] The diacid monomers are 1,4-cyclohexanedicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 1,4-naphthalenedicarboxylic acid, and 4,4'-dicarboxylic acid biphenyl sulfone.

[0059] The present invention has the following beneficial effects:

[0060] I. Triarylamine compounds are propeller-shaped molecules. Due to their non-planarity, they can suppress intermolecular stacking, thereby improving polymer solubility and enabling the formation of stable and uniform thin films. The central nitrogen atom is easily oxidized at lower voltages to form stable cationic free radicals, thus improving cycle stability. The triphenylamine polyamide containing naphthofuran in this invention, due to its direct bond with diphenylamine, reduces interchain stacking, significantly improving polymer solubility, and also enhancing electrochromic contrast and cycle stability.

[0061] II. The polymer of this invention exhibits excellent electrochromic properties; the triphenylamine unit contains active features of hole transport and electron transition, and when a certain range of voltage is applied to the polymer, the triphenylamine portion within the polyamide undergoes an oxidation reaction, thereby producing a color change. The polymer of this invention shows significant color changes within a voltage range of 0-1.3V, with the color changing from pale yellow to grayish-black.

[0062] 3. The polymer P1 of the present invention has strong fluorescence. When the polymer of the present invention comes into contact with a solution prepared with the explosive 2,4,6-trinitrophenol (TNP), the fluorescence of the polymer gradually decreases until it disappears. The polymer of the present invention can be used to detect the explosive 2,4,6-trinitrophenol.

[0063] IV. The polymer of this invention exhibits excellent memory performance; the device structure is ITO / PAs / Al. When the voltage is swept from 0 to -8V, the current suddenly increases and the resistance decreases sharply, indicating that the memory device undergoes a transition from the off state (HRS) to the on state (LRS), corresponding to the "write" process of a data storage device. It can then be "erased" and restored, meaning this device is a flash memory-type memristor that can be repeatedly written to and read from. Attached Figure Description

[0064] Figure 1 The NMR spectra of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine) monomers prepared in Examples 1 to 4 are shown below.

[0065] Figure 2 The following are the C NMR spectra of the N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine) monomers prepared in Examples 1 to 4;

[0066] Figure 3 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P1 containing naphthofuran prepared in Example 1;

[0067] Figure 4 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P2 containing naphthofuran prepared in Example 2;

[0068] Figure 5 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P3 containing naphthofuran prepared in Example 3;

[0069] Figure 6 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P4 containing naphthofuran prepared in Example 4;

[0070] Figure 7 Cyclic voltammetry diagrams of triphenylamine polyamides containing naphthofuran prepared in Examples 1 to 4;

[0071] Figure 8 Electrochromic image of triphenylamine polyamide P1 containing naphthofuran prepared in Example 1;

[0072] Figure 9 Electrochromic image of triphenylamine polyamide P2 containing naphthofuran prepared in Example 2;

[0073] Figure 10 Electrochromic image of triphenylamine polyamide P3 containing naphthofuran prepared in Example 3;

[0074] Figure 11 Electrochromic image of triphenylamine polyamide P3 containing naphthofuran prepared in Example 4;

[0075] Figure 12 Thermogravimetric curves of the triphenylamine polyamide polymers containing naphthofuran prepared in Examples 1 to 4 are shown.

[0076] Figure 13 The fluorescence spectrum of the triphenylamine polyamide polymer containing naphthol and furan prepared in Example 1 in response to TNP;

[0077] Figure 14 This is a schematic diagram of the structure of a memristor device containing naphthofuran-containing triphenylamine polyamide.

[0078] Figure 15 The current-voltage detection diagram of a memristor fabricated with a P1 thin film is shown.

[0079] Figure 16 The current-voltage detection diagram of a memristor fabricated with a P2 thin film is shown.

[0080] Figure 17 The current-voltage detection diagram of a memristor fabricated with a P3 thin film is shown.

[0081] Figure 18This is a current-voltage detection graph of a memristor fabricated using a P4 thin film. Detailed Implementation

[0082] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

[0083] Specific implementation method one: The triphenylamine polyamide containing naphthofuran in this implementation method is a triphenylamine polyamide containing naphthofuran, such as P1, P2, P3 or P4.

[0084] The structural formula of the triphenylamine polyamide P1 containing naphthofuran is as follows:

[0085]

[0086] In the formula, n is an integer from 3 to 20;

[0087] The structural formula of the triphenylamine polyamide P2 containing naphthofuran is as follows:

[0088]

[0089] In the formula, n is an integer from 3 to 20;

[0090] The structural formula of the triphenylamine polyamide P3 containing naphthofuran is as follows:

[0091]

[0092] In the formula, n is an integer from 3 to 20.

[0093] The structural formula of the triphenylamine polyamide P4 containing naphthofuran is as follows:

[0094]

[0095] In the formula, n is an integer from 3 to 20.

[0096] The triphenylamine polyamide containing naphthofuran prepared in this embodiment has significantly improved polymer solubility due to the presence of triphenylamine, which reduces inter-chain stacking. It also improves the contrast and cycling stability of electrochromic properties.

[0097] Specific Implementation Method Two: The preparation method of the triphenylamine polyamide containing naphthofuran in this implementation method is as follows:

[0098] I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer:

[0099] ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine if the reaction was complete. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water, followed by filtration and rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, named M1.

[0100] The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1;

[0101] The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL.

[0102] The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0103] ② Add M1 and liquid bromine to a three-necked flask, incubate in chloroform solution on an ice bath for 2 hours, then move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow, and chloroform is used for extraction. An appropriate amount of anhydrous sodium sulfate is added to the organic layer for drying; then, the mixture is filtered and the crude product is obtained by rotary evaporation. Next, recrystallization is performed using chloroform, and the product is dried under vacuum to obtain a white solid product, named M2.

[0104] In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5;

[0105] In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL.

[0106] The temperature of the cold water mentioned in step 1② is 0℃;

[0107] The room temperature mentioned in step 1② is 25℃;

[0108] The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0109] ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6 ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporation of the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3.

[0110] The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2;

[0111] In step 1③, the molar ratio of M2 to potassium carbonate is 1:7;

[0112] The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1;

[0113] In step 1③, the molar ratio of M2 to copper powder is 1:7;

[0114] In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol;

[0115] The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol;

[0116] The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0117] ④ At room temperature, anhydrous ethanol, Pd / C, and M3 were added to a three-necked flask. N2 was introduced into the three-necked flask, and hydrazine hydrate was added dropwise to the mixed solution in the three-necked flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, the heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, saturated sodium chloride solution was added until no solid phase was precipitated. The solid phase was filtered out and washed with water. Then, the mixture was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4.

[0118] The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol;

[0119] In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol.

[0120] In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute.

[0121] The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol;

[0122] The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4);

[0123] The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C;

[0124] The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%.

[0125] The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0126] II. Preparation of triphenylamine polyamides containing naphthofuran:

[0127] M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor.

[0128] The molar ratio of M4 to the diacid monomer in step two is 1:1;

[0129] The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0130] The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0131] The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0132] The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL;

[0133] In step two, the ratio of the volume of methanol added to the amount of M4 during the precipitation of solid is (200-250) mL: 1 mmol.

[0134] The diacid monomers are 1,4-cyclohexanedicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 1,4-naphthalenedicarboxylic acid, and 4,4'-dicarboxylic acid biphenyl sulfone.

[0135] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 2 in that: the solvent used in step 1① thin-layer chromatography is a mixture of ethyl acetate and petroleum ether, with a volume ratio of ethyl acetate to petroleum ether of 1:12; the solvent used in step 1③ thin-layer chromatography is a mixture of ethyl acetate and petroleum ether, with a volume ratio of ethyl acetate to petroleum ether of 1:12. Everything else is the same as in Specific Implementation Method 2.

[0136] Specific Implementation Method Four: This implementation method differs from Specific Implementation Method Two or Three in that the ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step one ① is 18 mmol:(300-400 mL). Everything else is the same as in Specific Implementation Method Two or Three.

[0137] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods Two to Four in that the molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step one ① is 1:1. Everything else is the same as in Specific Implementation Methods Two to Four.

[0138] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods Two to Five in that: step one ② uses chloroform for recrystallization; the recrystallization in step one ③ uses a mixed solution of dimethyl sulfoxide and ethanol, with a volume ratio of dimethyl sulfoxide to ethanol of 1:3. Everything else is the same as in Specific Implementation Methods Two to Five.

[0139] The difference between this embodiment and specific embodiments two to six is ​​that: in step two, Soxhlet extraction is performed using methanol and acetone for 72 hours; the volume ratio of methanol and acetone to the molar ratio of polyamide is 300 mL: 1 mmol. Everything else is the same as in specific embodiments two to six.

[0140] Specific Implementation Method 8: This implementation method describes the application of triphenylamine polyamide containing naphthofuran as an electrochromic layer in an electrochromic device.

[0141] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Method Eight in that the application of triphenylamine polyamide containing naphthofuran as the electrochromic layer in an electrochromic device is carried out according to the following steps:

[0142] A triphenylamine polyamide containing naphthofuran is used as the electrochromic layer in the electrochromic device. The electrochromic layer is coated on a transparent conductive substrate to form an active electrode, which generates electrochromism under the action of an external electric field. Everything else is the same as in Specific Embodiment Eight.

[0143] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Method Nine in that the transparent conductive substrate is conductive glass or a transparent conductive electrode. Everything else is the same as in Specific Implementation Method Nine.

[0144] Specific Implementation Method Eleven: This implementation method differs from Specific Implementation Method Nine or Ten in that the voltage of the applied electric field is 0–1.3V. Everything else is the same as in Specific Implementation Method Nine or Ten.

[0145] The beneficial effects of the present invention are verified using the following embodiments:

[0146] Example 1: The structural formula of triphenylamine polyamide P1 containing naphthofuran is as follows:

[0147]

[0148] In the formula, n is an integer from 3 to 20;

[0149] The preparation method of triphenylamine polyamide P1 containing naphthofuran in this embodiment is as follows:

[0150] I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer:

[0151] ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine if the reaction was complete. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water, followed by filtration and rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, named M1.

[0152] The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1;

[0153] The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL.

[0154] The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0155] ② Add M1 and liquid bromine to a three-necked flask, incubate in chloroform solution on an ice bath for 2 hours, then move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow, and chloroform is used for extraction. An appropriate amount of anhydrous sodium sulfate is added to the organic layer for drying; then, the mixture is filtered and the crude product is obtained by rotary evaporation. Next, recrystallization is performed using chloroform, and the product is dried under vacuum to obtain a white solid product, named M2.

[0156] In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5;

[0157] In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL.

[0158] The temperature of the cold water mentioned in step 1② is 0℃;

[0159] The room temperature mentioned in step 1② is 25℃;

[0160] The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0161] ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6 ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporation of the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3.

[0162] The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2;

[0163] In step 1③, the molar ratio of M2 to potassium carbonate is 1:7;

[0164] The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1;

[0165] In step 1③, the molar ratio of M2 to copper powder is 1:7;

[0166] In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol;

[0167] The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol;

[0168] The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0169] ④ At room temperature, anhydrous ethanol, Pd / C, and M3 were added to a three-necked flask. N2 was introduced into the three-necked flask, and hydrazine hydrate was added dropwise to the mixed solution in the three-necked flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, the heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, saturated sodium chloride solution was added until no solid phase was precipitated. The solid phase was filtered out and washed with water. Then, the mixture was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4.

[0170] The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol;

[0171] In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol.

[0172] In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute.

[0173] The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol;

[0174] The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4);

[0175] The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C;

[0176] The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%.

[0177] The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0178] II. Preparation of triphenylamine polyamides containing naphthofuran:

[0179] M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor.

[0180] The molar ratio of M4 to 1,4-cyclohexanedicarboxylic acid monomer in step two is 1:1;

[0181] The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0182] The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0183] The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0184] The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL;

[0185] In step two, the ratio of the volume of methanol added to the amount of M4 during the precipitation of solid is (200-250) mL: 1 mmol.

[0186] Example 2: The structural formula of triphenylamine polyamide P2 containing naphthofuran is as follows:

[0187]

[0188] In the formula, n is an integer from 3 to 20;

[0189] The preparation method of triphenylamine polyamide P2 containing naphthofuran in this embodiment is as follows:

[0190] I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer:

[0191] ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine if the reaction was complete. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water, followed by filtration and rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, named M1.

[0192] The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1;

[0193] The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL.

[0194] The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0195] ② Add M1 and liquid bromine to a three-necked flask, incubate in chloroform solution on an ice bath for 2 hours, then move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow, and chloroform is used for extraction. An appropriate amount of anhydrous sodium sulfate is added to the organic layer for drying; then, the mixture is filtered and the crude product is obtained by rotary evaporation. Next, recrystallization is performed using chloroform, and the product is dried under vacuum to obtain a white solid product, named M2.

[0196] In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5;

[0197] In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL.

[0198] The temperature of the cold water mentioned in step 1② is 0℃;

[0199] The room temperature mentioned in step 1② is 25℃;

[0200] The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0201] ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6 ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporation of the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3.

[0202] The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2;

[0203] In step 1③, the molar ratio of M2 to potassium carbonate is 1:7;

[0204] The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1;

[0205] In step 1③, the molar ratio of M2 to copper powder is 1:7;

[0206] In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol;

[0207] The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol;

[0208] The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0209] ④ At room temperature, anhydrous ethanol, Pd / C, and M3 were added to a three-necked flask. N2 was introduced into the three-necked flask, and hydrazine hydrate was added dropwise to the mixed solution in the three-necked flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, the heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, saturated sodium chloride solution was added until no solid phase was precipitated. The solid phase was filtered out and washed with water. Then, the mixture was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4.

[0210] The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol;

[0211] In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol.

[0212] In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute.

[0213] The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol;

[0214] The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4);

[0215] The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C;

[0216] The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%.

[0217] The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0218] II. Preparation of triphenylamine polyamides containing naphthofuran:

[0219] M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor.

[0220] The molar ratio of M4 to 4,4'-dicarboxylic diphenyl ether monomer in step two is 1:1;

[0221] The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0222] The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0223] The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0224] The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL;

[0225] In step two, the ratio of the volume of methanol added to the amount of M5 during the precipitation of solid is (200-250) mL: 1 mmol.

[0226] Example 3: The structural formula of triphenylamine polyamide P3 containing naphthofuran is as follows:

[0227]

[0228] In the formula, n is an integer from 3 to 20.

[0229] The preparation method of triphenylamine polyamide P3 containing naphthofuran in this embodiment is as follows:

[0230] I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer:

[0231] ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine if the reaction was complete. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water, followed by filtration and rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, named M1.

[0232] The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1;

[0233] The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL.

[0234] The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0235] ② Add M1 and liquid bromine to a three-necked flask. After 2 hours of ice bath in chloroform solution, move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow, and extraction is performed. An appropriate amount of anhydrous sodium sulfate is added to the organic layer for drying; then, the mixture is filtered and the crude product is obtained by rotary evaporation. Next, recrystallization is performed using chloroform (CHCl3), and the product is dried under vacuum to obtain a white solid product, named M2.

[0236] In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5;

[0237] In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL.

[0238] The temperature of the cold water mentioned in step 1② is 0℃;

[0239] The room temperature mentioned in step 1② is 25℃;

[0240] The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0241] ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6 ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporation of the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3.

[0242] The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2;

[0243] In step 1③, the molar ratio of M2 to potassium carbonate is 1:7;

[0244] The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1;

[0245] In step 1③, the molar ratio of M2 to copper powder is 1:7;

[0246] In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol;

[0247] The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol;

[0248] The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0249] ④ At room temperature, anhydrous ethanol, Pd / C, and M4 were added to a three-necked flask. N2 was introduced into the three-necked flask, and hydrazine hydrate was added dropwise to the mixed solution in the three-necked flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, the heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, saturated sodium chloride solution was added until no solid phase was precipitated. The solid phase was filtered out and washed with water. Then, the mixture was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4.

[0250] The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol;

[0251] In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol.

[0252] In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute.

[0253] The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol;

[0254] The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4);

[0255] The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C;

[0256] The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%.

[0257] The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0258] II. Preparation of triphenylamine polyamides containing naphthofuran:

[0259] M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor.

[0260] The molar ratio of M4 to 1,4-naphthalenedicarboxylic acid monomer in step two is 1:1;

[0261] The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0262] The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0263] The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0264] The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL;

[0265] In step two, the ratio of the volume of methanol added to the amount of M5 during the precipitation of solid is (200-250) mL: 1 mmol.

[0266] Example 4: The structural formula of triphenylamine polyamide P4 containing naphthofuran is as follows:

[0267]

[0268] In the formula, n is an integer from 3 to 20.

[0269] The preparation method of triphenylamine polyamide P4 containing naphthofuran in this embodiment is as follows:

[0270] I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer:

[0271] ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine if the reaction was complete. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water, followed by filtration and rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, named M1.

[0272] The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1;

[0273] The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL.

[0274] The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0275] ② Add M1 and liquid bromine to a three-necked flask, incubate in chloroform solution on an ice bath for 2 hours, then move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow, and chloroform is used for extraction. An appropriate amount of anhydrous sodium sulfate is added to the organic layer for drying; then, the mixture is filtered and the crude product is obtained by rotary evaporation. Next, recrystallization is performed using chloroform, and the product is dried under vacuum to obtain a white solid product, named M2.

[0276] In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5;

[0277] In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL.

[0278] The temperature of the cold water mentioned in step 1② is 0℃;

[0279] The room temperature mentioned in step 1② is 25℃;

[0280] The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0281] ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6 ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporation of the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3.

[0282] The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2;

[0283] In step 1③, the molar ratio of M2 to potassium carbonate is 1:7;

[0284] The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1;

[0285] In step 1③, the molar ratio of M2 to copper powder is 1:7;

[0286] In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol;

[0287] The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol;

[0288] The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0289] ④ At room temperature, anhydrous ethanol, Pd / C, and M4 were added to a three-necked flask. N2 was introduced into the three-necked flask, and hydrazine hydrate was added dropwise to the mixed solution in the three-necked flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, the heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, saturated sodium chloride solution was added until no solid phase was precipitated. The solid phase was filtered out and washed with water. Then, the mixture was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4.

[0290] The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol;

[0291] In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol.

[0292] In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute.

[0293] The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol;

[0294] The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4);

[0295] The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C;

[0296] The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%.

[0297] The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa;

[0298] II. Preparation of triphenylamine polyamides containing naphthofuran:

[0299] M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor.

[0300] The molar ratio of M4 to 4,4'-dicarboxybiphenyl sulfone monomer in step two is 1:1;

[0301] The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0302] The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0303] The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol;

[0304] The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL;

[0305] In step two, the ratio of the volume of methanol added to the amount of M4 during the precipitation of solid is (200-250) mL: 1 mmol.

[0306] In Examples 1 to 4, the solvent used in step 1① of the thin-layer chromatography was a mixture of ethyl acetate and petroleum ether, with a volume ratio of ethyl acetate to petroleum ether of 1:12; the solvent used in step 1④ of the thin-layer chromatography was also a mixture of ethyl acetate and petroleum ether, with a volume ratio of ethyl acetate to petroleum ether of 1:12. The molar ratio of 1,1'-bi-2-naphthol to toluene in step 1① was 18 mmol:(300-400 mL); the molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① was 1:1. Other aspects were the same as in any of Examples 2 to 4. Step 1② involved recrystallization using chloroform; the recrystallization in step 1③ involved recrystallization using a mixture of dimethyl sulfoxide and ethanol, with a volume ratio of dimethyl sulfoxide to ethanol of 1:3. Step 2, the Soxhlet extraction, involved extraction with methanol and acetone for 72 hours; the volume ratio of methanol / acetone to M5 was 300 mL:1 mmol.

[0307] The triphenylamine polyamides containing naphthofuran prepared in Examples 1 to 4 exhibit significantly enhanced color-changing effects and greatly improved cycle stability due to the direct linkage between diphenylamine and naphthofuran, which reduces interchain stacking. Therefore, the naphthofuran-containing triphenylamine polyamides prepared in this invention, by introducing triphenylamine, increase the solubility of the polyamide, making it readily soluble in polar solvents, with 0.1–0.15 g of polymer soluble in each 1 mL of polar solution.

[0308] The preparation method of the triphenylamine polyamide containing naphthol and furan as an electrochromic material in Examples 1 to 4 is as follows: 1 mg of triphenylamine polyamide containing naphthol and furan is dissolved in 1 mL of organic solvent to obtain a triphenylamine polyamide solution containing naphthol and furan. Then, the triphenylamine polyamide containing naphthol and furan is coated on conductive glass to obtain an electrochromic material. The organic solvent is N-methylpyrrolidone.

[0309] Figure 1 The NMR spectra of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine) monomers prepared in Examples 1 to 4 are shown below.

[0310] Figure 2 The images show the C NMR spectra of the N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine) monomers prepared in Examples 1 to 4, indicating that the N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine) monomers were synthesized in Examples 1 to 4.

[0311] Figure 3 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P1 containing naphthofuran prepared in Example 1;

[0312] Figure 4 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P2 containing naphthofuran prepared in Example 2;

[0313] Figure 5 The hydrogen nuclear magnetic resonance spectrum of the triphenylamine polyamide P3 containing naphthofuran prepared in Example 3;

[0314] Figure 6 The photon nuclear magnetic resonance (NMR) spectrum of the triphenylamine polyamide P4 containing naphthofuran prepared in Example 3 is shown.

[0315] from Figure 2-5 As can be seen from the figure, the chemical shift δ is 6.68 to 8.23 ​​ppm, which is the chemical shift of H on the aromatic ring; the chemical shift δ is 9.80 to 10.58, which is the chemical shift of H on the amide group, indicating that the triphenylamine polyamide containing naphthol was synthesized in Examples 1 to 4.

[0316] Figure 7 Cyclic voltammetry diagrams of triphenylamine polyamides containing naphthofuran prepared in Examples 1 to 4; from Figure 6It can be seen that P1 showed an oxidation peak at 0.997V and a reduction peak at 0.51V; P2 showed an oxidation peak at 0.976V and a reduction peak at 0.58V; P3 showed an oxidation peak at 0.928V and a reduction peak at 0.606V; P4 showed an oxidation peak at 1.042V and a reduction peak at 0.665V. This indicates that the triphenylamine polyamides containing naphthofuran prepared in Examples 1 to 4 underwent a redox reaction under applied voltage. During the redox process, the triphenylamine polyamides containing naphthofuran changed color, indicating that the triphenylamine polyamides containing naphthofuran prepared in Examples 1 to 4 have electrochromic properties.

[0317] Figure 8 Electrochromic image of triphenylamine polyamide P1 containing naphthofuran prepared in Example 1; Figure 9 Electrochromic image of triphenylamine polyamide P2 containing naphthofuran prepared in Example 2; Figure 10 Electrochromic image of triphenylamine polyamide P3 containing naphthofuran prepared in Example 3; Figure 11 The image shows the electrochromic spectrum of the triphenylamine polyamide P4 containing naphthofuran prepared in Example 4. As can be seen from the image, the UV-Vis spectrum of the PAs changes with increasing linearly applied voltage. Taking the electrochromic properties of P1 as an example... Figure 8 As shown, with increasing voltage, the absorption at 530nm, 602nm, and 890nm gradually increases between 0.0V and 1.2V; when applied to 1.2V, the film color turns grayish-black, and the absorption at the prominent wavelengths of 530nm and 890nm remains unchanged, indicating that TPA is completely oxidized to TPA. + .

[0318] Figure 12 Thermogravimetric curves of the triphenylamine polyamide polymers containing naphthofuran prepared in Examples 1 to 4 are shown. Figure 12 The results show that the triphenylamine polyamide polymers containing naphthofuran all exhibit thermal decomposition temperatures above 300℃ under a nitrogen atmosphere with a 5% weight loss, indicating good thermodynamic stability. When the polymer temperature is heated to 800℃, the residual carbon content is greater than 58%, due to the high content of aromatic structures. This further demonstrates the polymer's good thermal stability, enabling it to operate in high-temperature environments, such as aerospace and other high-temperature conditions.

[0319] Figure 13The fluorescence spectrum of the triphenylamine polyamide polymer containing naphthofuran prepared in Example 1 to TNP response; 1 mg of the triphenylamine polyamide polymer P1 containing naphthofuran groups was dissolved in 20 mL of N-methylpyrrolidone to obtain a concentration of 1×10 -5 M is a triphenylamine polyamide polymer solution containing naphthol and furan. 5 μL of TNP is added to the triphenylamine polyamide polymer solution containing naphthol and furan. The curves in the figure show the fluorescence intensity curves of the triphenylamine polyamide polymer solution containing naphthol and furan without added TNP and the fluorescence intensity curves of solutions with different concentrations of TNP added sequentially (5 μL each). Figure 13 It can be seen that as the TNP concentration increases, the fluorescence intensity of the polymer solution gradually weakens; this indicates that the polymer can respond to TNP, and the presence of TNP can be determined by whether the fluorescence of the polymer solution decreases.

[0320] Figure 14 The schematic diagram shows the structure of a memristor device containing naphthofuran and triphenylamine polyamide. The specific method is as follows:

[0321] (1) A 1 mg / ml polyamide solution was dropped onto a 20 mm × 30 mm ITO glass plate, using N-methylpyrrolidone as the solvent. The plate was then dried in a vacuum oven at 100 °C to form a film.

[0322] (2) Use a vacuum evaporation machine to deposit aluminum electrodes on the polymer film.

[0323] (3) Test its current performance by using a voltage of -8 to 8V between aluminum and ITO.

[0324] Figure 15 The image shows the current-voltage sensing plot of a memristor fabricated with a P1 thin film. At -3.05V, the device exhibits a sudden increase in current and a sharp decrease in resistance, with the switching current ratio reaching 10. 3 This is the writing process, which can be restored afterwards. That is, the device is a flash memory memristor that can be repeatedly written and read. Figure 16 The image shows the current-voltage sensing plot of a memristor fabricated with a P2 thin film. At -2.55V, the device exhibits a sudden increase in current and a sharp decrease in resistance, with the switching current ratio reaching 10. 3 This is the writing process, which can be restored afterwards. That is, the device is a flash memory memristor that can be repeatedly written and read. Figure 17 The image shows the current-voltage sensing plot of a memristor fabricated with a P3 thin film. At -2.9V, the device exhibits a sudden increase in current and a sharp decrease in resistance, with the switching current ratio reaching 10. 3 This is the writing process, which can be restored afterwards. That is, the device is a flash memory memristor that can be repeatedly written and read. Figure 18The image shows the current-voltage sensing of a memristor fabricated using a P4 thin film. At -2.5V, the device exhibits a sudden increase in current and a sharp decrease in resistance, with the switching current ratio reaching 10. 3 This is the writing process, which can be reversed afterward, meaning the device is a write-and-read flash memory memristor. This indicates that this type of polyamide is suitable for fabricating write-and-read flash memory memristors.

[0325] As shown in the above experiments, this embodiment synthesized and characterized N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine). Novel triphenylamine polyamides were generated by polycondensation of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) with different diacids. Due to the presence of propeller-shaped triphenylamine and methoxy groups in the main chain, all polyamides exhibit good solubility and excellent film-forming ability, along with high thermal stability. These polyamides show ideal results in the preparation of high-performance electrochromic materials, with the electrochromic layer changing from colorless to grayish-black after applying an external voltage. They can also be applied in the TNP detection of explosives. Furthermore, memristor devices were prepared using four types of polyamide films to test the application of this type of polyamide in the field of memory devices. Ultimately, a flash memory-type memristor capable of repeated writing and reading was obtained, and this memristor possesses 10... 3 The switching current ratio is high. Therefore, this work opens up a new avenue for developing high-performance electrochromic materials, explosives detection, and electrochemical storage materials, which will greatly promote the application of polyamides containing naphthalene and furan structures in the optoelectronic field.

Claims

1. Diamine monomers containing the structures of naphthofuran and triphenylamine. Its structural formula is as follows:

2. A polyamide synthesized from a monomer containing naphthalenefuran, characterized in that... Polyamides P1, P2, P3, and P4 are polymerized from diamine monomers containing naphthofuran and triphenylamine structures and diacid monomers as described in claim 1; the diacid monomer is HOOCAR(R)COOH, wherein AR(R) is an aromatic or alkyl group; The structural formula of the triphenylamine polyamide P1 containing naphthofuran is as follows: In the formula, n is an integer from 3 to 20; The structural formula of the triphenylamine polyamide P2 containing naphthofuran is as follows: In the formula, n is an integer from 3 to 20; The structural formula of the triphenylamine polyamide P3 containing naphthofuran is as follows: In the formula, n is an integer from 3 to 20; The structural formula of the triphenylamine polyamide P4 containing naphthofuran is as follows: In the formula, n is an integer from 3 to 20.

3. The method for preparing triphenylamine polyamide containing naphthofuran as described in claim 2, characterized in that... The preparation method is as follows: I. Synthesis of N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)phenyl-1,4-diamine) monomer: ① Under a nitrogen atmosphere, 1,1'-bi-2-naphthol, p-toluenesulfonic acid, and toluene solution were added to a three-necked flask. The mixture was then heated and stirred at a constant temperature of 160°C. Thin-layer chromatography was used to determine whether the isothermal reaction had ended. After the reaction, the solution was cooled to room temperature and quenched in a saturated potassium carbonate solution. The organic phase was then extracted with ethyl acetate. Anhydrous magnesium sulfate was added to remove water from the organic phase. The mixture was then filtered and rotary evaporated to obtain the crude product. The crude product was then separated by silica gel column chromatography and dried under vacuum to obtain a white solid, which was named M1. The molar ratio of 1,1'-bi-2-naphthol to p-toluenesulfonic acid in step 1① is 1:1; The ratio of the amount of 1,1'-bi-2-naphthol to the volume of toluene in step 1① is 18 mmol: 300 mL. The vacuum drying temperature in step 1① is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa; ② Add M1 and liquid bromine to a three-necked flask, incubate in an ice bath in chloroform solution for 2 hours, then move to room temperature and react for 12 hours. The resulting mixture is poured into a saturated sodium bisulfite solution to quench excess bromine. With continuous stirring, the solution changes from orange-red to pale yellow. Extract with chloroform, add an appropriate amount of anhydrous sodium sulfate to the organic layer, and dry. Then remove the solid by vacuum filtration and obtain the crude product by rotary evaporation. Next, recrystallize with chloroform and dry under vacuum to obtain a white solid product, named M2. In step 1②, the molar ratio of M1 to liquid bromine is 1:2.5; In step 1②, the ratio of the amount of substance M1 to the volume of chloroform is 7 mmol: 150 mL. The temperature of the cold water mentioned in step 1② is 0℃; The room temperature mentioned in step 1② is 25℃; The vacuum drying temperature described in step 1② is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa; ③ Under a N2 atmosphere, a mixture of M2, 4-methoxy-4'-nitrodiphenylamine, potassium carbonate, 18-crown-6-ether, copper powder, and o-dichlorobenzene was heated to 165°C and refluxed. After the reaction was completed, the mixture was filtered. The filtrate was added to petroleum ether to precipitate the precipitate, which was then filtered again. The solid obtained by filtration was purified by silica gel column chromatography. After evaporating the solution, it was dried under vacuum to obtain N5,N9-bis(4-methoxyphenyl)-N5,N9-bis(4-nitrophenyl)dinaphtho[2,1-b:1',2'-d]furan-5,9-diamine, named M3. The molar ratio of M2 to 4-methoxy-4'-nitrodiphenylamine in step 1③ is 1:2; In step 1③, the molar ratio of M2 to potassium carbonate is 1:7; The molar ratio of M2 to 18-crown-6 ether in step 1③ is 1:1; In step 1③, the molar ratio of M2 to copper powder is 1:7; In step 1③, the volume ratio of o-dichlorobenzene to the amount of M2 is 5 mL: 1 mmol; The volume ratio of petroleum ether to the amount of M2 in step 1③ is (150-200) mL: 1 mmol; The vacuum drying temperature described in step 1③ is 40℃, the vacuum drying time is 36 to 48 hours, and the vacuum drying pressure is -30 to -29 kPa; ④ At room temperature, anhydrous ethanol, Pd / C, and M3 were added to a three-necked flask. N2 was introduced into the three-necked flask, and hydrazine hydrate was added dropwise to the mixed solution in the three-necked flask at a rate of 1-2 drops per second using a constant pressure funnel. The temperature was raised to the boiling point of ethanol, and the reduction reaction was carried out for 10-14 hours. After the reaction was completed, the heating was stopped, the mixture was filtered, and the filtrate was poured into distilled water. Then, saturated sodium chloride solution was added until no solid phase was precipitated. The solid phase was filtered out and washed with water. Then, the mixture was dried under vacuum to obtain N1,N1'-(dinaphtho[2,1-b:1',2'-d]furan-5,9-diyl)bis(N1-(4-methoxyphenyl)benzene-1,4-diamine), which was named M4. The volume ratio of anhydrous ethanol to the amount of M3 in step 1, ④ is (100-120) mL: 1 mmol. In step 1, the mass ratio of Pd / C to the molar amount of M3 is 1 g: 5 mmol. In step 1, ④, the heating rate when heating to the boiling point of ethanol is approximately 10°C per minute. The volume ratio of hydrazine hydrate to the amount of M3 in step 1, ④ is 5 mL: 1 mmol; The volume ratio of the filtrate to distilled water in step 1, ④ is 1:(3-4); The cold sodium chloride solution mentioned in step 1, ④ is at approximately 0°C; The Pd / C mentioned in step 1④ is a Pd C-doped composite material, and the mass fraction of Pd in ​​Pd / C is 10%. The vacuum drying temperature described in step 1④ is 30℃, the vacuum drying time is 48 to 60 hours, and the vacuum drying pressure is -30 to -29 kPa; II. Preparation of triphenylamine polyamides containing naphthofuran: M4, diacid monomers, triphenyl phosphite, CaCl2, pyridine and N-methylpyrrolidone were mixed and stirred at 120°C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate solids. The product was collected by filtration, washed thoroughly with methanol and acetone, and finally extracted with methanol and acetone using a Soxhlet extractor. The molar ratio of M4 to the diacid monomer in step two is 1:1; The volume ratio of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL: 1 mmol; The volume ratio of pyridine to the molar amount of M4 in step two is 1.5 mL: 1 mmol; The volume ratio of N-methylpyrrolidone to the molar amount of M4 in step two is 1.5 mL: 1 mmol; The mass ratio of CaCl2 to the volume of N-methylpyrrolidone in step two is 0.15 g : 1.5 mL; In step two, the ratio of the volume of methanol added to the amount of M4 during the precipitation of solid is (200-250) mL: 1 mmol. The diacid monomers are 1,4-cyclohexanedicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 1,4-naphthalenedicarboxylic acid, and 4,4'-dicarboxylic acid biphenyl sulfone.

4. The method for preparing triphenylamine polyamide containing naphthofuran according to claim 3, characterized in that... In step two, Soxhlet extraction was performed using methanol and acetone for 72 hours; the volume ratio of methanol and acetone to the molar amount of polyamide was 300 mL: 1 mmol.

5. The application of the triphenylamine polyamide containing naphthofuran as described in claim 2 as an electrochromic layer in an electrochromic device.

6. The application of the triphenylamine polyamide containing naphthofuran according to claim 5, characterized in that: The application of triphenylamine polyamides containing naphthofuran as electrochromic layers in electrochromic devices is carried out according to the following steps: A triphenylamine polyamide containing naphthofuran is used as the electrochromic layer in an electrochromic device. The electrochromic layer is coated on a transparent conductive substrate to prepare an active electrode, which generates electrochromism under the action of an external electric field.

7. The application of the triphenylamine polyamide containing naphthofuran according to claim 6, characterized in that... The transparent conductive substrate is conductive glass or a transparent conductive electrode.

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