Hyperbranched polyamides containing methylpiperazine and polytriphenylamine structures, methods of making and uses thereof

Abstract

Hyperbranched polyamides containing methylpiperazine and polytriphenylamine structures, and preparation method and application thereof. The present application relates to a monomer containing methylpiperazine and triphenylamine core: N1, N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazine-1-yl)phenyl)phenyl-1,4-diamine, and a preparation method and application of hyperbranched polyamides. In order to solve the problems of low solubility in organic solvents, poor thermal stability, single color change, low optical contrast and poor electrochemical stability of triphenylamine-based polyamide materials, methylpiperazine electron-donating groups and multiple electroactive centers are introduced in the molecular design process, and hyperbranched polyamides are synthesized, which increase the color change ability and cycle stability of the polymer. The solubility of the hyperbranched polyamide is significantly improved, and at the same time, it has excellent electrochromic performance, including excellent cycle stability, multiple color changes and high optical contrast. The present application is applied to the fields of electrochromic display, sensing and photoelectric detection.

Description

TECHNICAL FIELD

[0001] The present application relates to a hyperbranched polyamide containing methylpiperazine and multi-triphenylamine structure and its preparation method and application. BACKGROUND

[0002] As a color-related electro-stimulus response material, electrochromic materials have attracted the attention of many researchers due to their rich color change, high optical contrast before and after color change, and relatively low price. At present, they have been applied in intelligent windows, electronic tags and goggles, etc. Among them, the intelligent window through color change to adjust indoor light and temperature has become an important part of the building and automobile industry to achieve energy saving, in order to cope with the uncontrollability and periodic tension of energy supply. Triphenylamine is a spiral-shaped molecule with high redox activity and excellent cationic stability. Derivatives or polymers based on triphenylamine are widely used in electrochromic materials. In addition, the introduction of electron-donating groups on the para position of triphenylamine units can reduce the oxidation potential and improve the electrochemical stability. Multi-triphenylamine structure can improve the thermal performance of the polymer, and also can realize multiple color change in photoelectrochemistry and exhibit obvious near-infrared absorption in optics. Based on the electron-donating methylpiperazine group, this patent constructs a multi-triphenylamine structure to synthesize a new type of hyperbranched polyamide, in order to obtain an electrochromic material and device with good solubility, easy film formation, strong stability, multiple color change and high optical contrast. SUMMARY

[0003] The purpose of the present application is to solve the problems of triphenylamine-based polyamide electrochromic materials, such as poor solubility in organic solvents, poor thermal stability, single color change, low optical contrast and poor electrochemical stability, etc. A hyperbranched polyamide containing methylpiperazine and multi-triphenylamine structure and its preparation method and application in electrochromic are proposed. The hyperbranched polyamide structure obtained by condensation of diamine monomers containing methylpiperazine and multi-triphenylamine structure and commercially available diacid monomers (including but not limited to 1,4-cyclohexane dicarboxylic acid, 4,4-diphenylsulfonyl dicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether and 2,2-bis(4-carboxyphenyl) hexafluoropropane, 4,4'-diphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid, 3,4-thiophene dicarboxylic acid, 3,4-furan dicarboxylic acid, succinic acid, etc.) is as follows:

[0004]

[0005] In the formula, the branching degree is 0.50-0.81.

[0006] 2, The preparation method of the hyperbranched polyamide containing methylpiperazine and multi-triphenylamine structure according to the present application is carried out according to the following steps:

[0007] I. Synthesis of N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazin-1-yl)phenyl)phenyl-1,4-diamine monomer:

[0008] ①, under N2 atmosphere, 4-(4-methylpiperazin) aniline monomer, cesium fluoride, p-fluoroniitrobenzene and dimethyl sulfoxide were placed in a three-necked flask, the system was heated to 120℃ for reflux reaction, after the reaction was judged to be completed by thin layer chromatography, the heat source was turned off; the cooled mixture was poured into a mixed solution of deionized water and ethanol until the crude product was precipitated, filtered, and the crude product was recrystallized with methanol, filtered again, and the obtained product was vacuum dried to obtain red powder M1;

[0009] The volume ratio of dimethyl sulfoxide to the amount of substance of 4-(4-methylpiperazin) aniline monomer in step one ① is (50-100) mL: 10 mmol;

[0010] The amount of substance ratio of cesium fluoride to 4-(4-methylpiperazin) aniline monomer in step one ① is 2.2:1;

[0011] The molar ratio of p-fluoroniitrobenzene to 4-(4-methylpiperazin) aniline monomer in step one ① is 2.2:1;

[0012] The temperature of vacuum drying in step one ① is 45℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is -30 to -29 KPa;

[0013] ②, under room temperature conditions, anhydrous ethanol, Pd / C and M1 were added to a three-necked flask and stirred; under N2 conditions, hydrazine hydrate was added to the three-necked flask at a drop rate of 1-2 drops per second using a constant pressure funnel; the system was heated to 80℃ to reflux the solution, and after the reaction was completed, Pd / C was removed by hot filtration, and the filtrate was poured into salt water under stirring, extracted with dichloromethane solvent for 3 times; the obtained organic phase solution was dried with anhydrous magnesium sulfate to remove water, filtered to obtain a transparent solution; the filtrate was rotary evaporated, vacuum dried to obtain a grayish white monomer M2;

[0014] The volume ratio of anhydrous ethanol to the amount of substance of M1 in step one ② is (150-200) mL: 10 mmol;

[0015] The mass ratio of Pd / C to the amount of substance of M1 in step one ② is (1-1.2) g: 5 mmol;

[0016] The volume ratio of hydrazine hydrate to the amount of substance of M1 in step one ② is 2.5 mL: 1 mmol;

[0017] The Pd / C in step 1(2) is a C-doped composite material of Pd, and the mass fraction of Pd in Pd / C is 5%;

[0018] The temperature of vacuum drying in step 1(2) is 30℃, the time of vacuum drying is 48-64 hours, and the pressure of vacuum drying is -30 to -29 KPa;

[0019] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0020] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0021] In step 1(3), the volume ratio of dimethyl sulfoxide to the amount of substance of M2 is (50-100) mL: 10 mmol.

[0022] In step 1(3), the amount of substance ratio of cesium fluoride to M2 is 4.8:1.

[0023] In step 1(3), the amount of substance ratio of cesium fluoride to M2 is 4.8:1.

[0024] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0025] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0026] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0027] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0028] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0029] In step 1(3), M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step 1(1).

[0030] The ratio of the substance amount of M4 to the diacid monomer in step two is 1:2;

[0031] The ratio of the volume of the triphenyl phosphite to the substance amount of M4 in step two is 1.5 mL: 1 mmol;

[0032] The ratio of the volume of the pyridine to the substance amount of M4 in step two is 1.5 mL: 1 mmol;

[0033] The ratio of the volume of the N-methyl pyrrolidone to the substance amount of M4 in step two is 3 mL: 1 mmol;

[0034] The ratio of the mass of the CaCl2 to the volume of the N-methyl pyrrolidone in step two is 0.3 g: 6 mL;

[0035] The ratio of the volume of the methanol to the substance amount of M4 in step two is 350 mL: 1 mmol.

[0036] The hyperbranched polyamide containing a methyl piperazine and a polytriphenylamine structure is applied to the electrochromic field as an electrochromic material.

[0037] The polyamide material with excellent electrochromic comprehensive ability is prepared, and the problems of poor solubility, poor thermal stability, single electrochromic, low optical contrast and electrochromic instability of the polyamide are improved by introducing a plurality of triphenylamine units with a spiral structure and a methyl piperazine alkyl chain to further synthesize a hyperbranched structure.

[0038] The present application has the following beneficial effects:

[0039] The hyperbranched polyamide containing methyl piperazine and multi-triphenylamine structure has significantly improved solubility and thermal stability due to the hyperbranched structure and the introduction of multi-triphenylamine units. It is easily soluble in polar solvents, 0.1-0.2 grams per milliliter of polar solvent; the thermal stability of the hyperbranched polyamide is evaluated by thermal gravimetric test under N2 atmosphere, the hyperbranched polyamide containing methyl piperazine and multi-triphenylamine structure starts to lose weight at 320℃; when the temperature is 800℃, the carbon residue rate is 47-61%, the results show that the hyperbranched polyamide containing methyl piperazine and multi-triphenylamine structure has good solubility and thermal stability.

[0040] Two, the polymer has excellent electrochromic performance

[0041] Electrochromism refers to the phenomenon that a substance undergoes electrochemical redox reaction under the driving of external voltage or current, that is, under the action of an external electric field, the transmittance of the substance in the visible light range produces stable and reversible change. The polymer of the present application has multiple color changes in the electrochromic process, the polymers P1-P4 gradually change from colorless to yellow-green, light blue and dark blue; the optical contrast is high, among which the optical contrast of polymer P1 can reach up to 77%; in addition, the polymer has good cycle stability, the optical contrast of polymer P2 is retained by 80% under 3720 cycles, showing excellent electrochromic stability. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 The hydrogen nuclear magnetic spectrum of N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazine-1-yl)phenyl)phenyl-1,4-diamine monomer (M4) prepared in Example One;

[0043] Figure 2 The Fourier infrared spectra of four kinds of hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples One to Four;

[0044] Figure 3 The cyclic voltammograms of four kinds of hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples One to Four;

[0045] Figure 4 The thermogravimetric analysis spectra of the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples One to Four;

[0046] Figure 5 The ultraviolet-visible-near infrared absorption spectra of four kinds of hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples One to Four;

[0047] Figure 6The electrochromic cyclic stability diagram of the hyperbranched polyamide P1 containing methyl piperazine and polytriphenylamine structure prepared in Example 1.

[0048] Figure 7 The electrochromic device mechanism diagram of the hyperbranched polyamide P1 film containing methyl piperazine and polytriphenylamine structure prepared in Example 1. DETAILED DESCRIPTION

[0049] The technical solution of the present application is not limited to the following specific embodiments, but also includes any reasonable combination between the specific embodiments.

[0050] Specific embodiment one: the structural formula of the monomer and the hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure in the present embodiment are as follows:

[0051]

[0052]

[0053] , wherein the branching degree is 0.50-0.81.

[0054] The present application has the following beneficial effects:

[0055] First, the hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure has significantly improved solubility and thermal stability due to the introduction of hyperbranched structure and polytriphenylamine unit. It is easily soluble in polar solvents, 0.1-0.2 grams per milliliter of polar solvent; the thermal stability of the hyperbranched polyamide is evaluated by thermal gravimetric test under N2 atmosphere, the hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure starts to lose weight at 320℃; when the temperature is 800℃, the carbon residue rate is 47-61%, which shows that the hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure has good solubility and thermal stability.

[0056] Second, the polymer has excellent electrochromic performance

[0057] Electrochromism refers to the phenomenon that a substance undergoes electrochemical oxidation-reduction reaction under the driving of an external voltage or current, causing color change. That is, under the action of an external electric field, the transmittance of the substance produces stable reversible change in the visible light range. The polymer of the present application has multiple color changes in the electrochromic process, the polymers P1-P4 gradually change from colorless to yellow-green, light blue and dark blue; the optical contrast is high, among which the optical contrast of polymer P1 can be as high as 77%; in addition, the polymer has good cyclic stability, the optical contrast of polymer P2 is retained by 80% after 3720 cycles, showing excellent electrochromic stability.

[0058] Specific embodiment two: the preparation method of the monomer and hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure is carried out according to the following steps:

[0059] I. Synthesis of N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazine-1-yl)phenyl)phenyl-1,4-diamine monomer:

[0060] ①, under N2 atmosphere, 4-(4-methylpiperazine) aniline monomer, cesium fluoride, p-fluoroniitrobenzene and dimethyl sulfoxide are placed in a three-necked flask, the system is heated to 120℃ for reflux reaction, and the reaction is judged to be completed by thin layer chromatography. After the heat source is turned off, the cooled mixture is poured into a mixed solution of deionized water and ethanol until the crude product is precipitated, filtered, and then recrystallized with methanol. The crude product is filtered again, and the obtained product is vacuum dried to obtain a red powder M1;

[0061] The volume ratio of dimethyl sulfoxide to the amount of substance of 4-(4-methylpiperazine) aniline monomer in step one ① is (50-100) mL: 10 mmol;

[0062] The amount of substance ratio of cesium fluoride to 4-(4-methylpiperazine) aniline monomer in step one ① is 2.2:1;

[0063] The molar ratio of p-fluoroniitrobenzene to 4-(4-methylpiperazine) aniline monomer in step one ① is 2.2:1;

[0064] The temperature of vacuum drying in step one ① is 45℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is -30 to -29 KPa;

[0065] ②, under room temperature conditions, anhydrous ethanol, Pd / C and M1 are added to a three-necked flask and stirred; under N2 conditions, hydrazine hydrate is added to the three-necked flask at a drop rate of 1-2 drops per second using a constant pressure funnel; the system is heated to 80℃ to reflux the solution, and after the reaction is completed, Pd / C is removed by hot filtration. The filtrate is poured into salt water under stirring, extracted with dichloromethane solvent for 3 times; the obtained organic phase solution is dried with anhydrous magnesium sulfate to remove water, filtered to obtain a transparent solution; the filtrate is rotary evaporated, vacuum dried to obtain a grayish white monomer M2;

[0066] The volume ratio of anhydrous ethanol to the amount of substance of M1 in step one ② is (150-200) mL: 10 mmol;

[0067] The mass ratio of Pd / C to the amount of substance of M1 in step one ② is (1-1.2) g: 5 mmol;

[0068] The ratio of the volume of hydrazine hydrate to the amount of substance of M1 in step one ② is 2.5 mL: 1 mmol;

[0069] The Pd / C in step one ② is a C-doped composite material of Pd, and the mass fraction of Pd in Pd / C is 5%;

[0070] The temperature of vacuum drying in step one ② is 30℃, the time of vacuum drying is 48-64 hours, and the pressure of vacuum drying is -30 to -29 KPa;

[0071] ③, the specific preparation method of M3 is the same as step one ①, with several differences as follows:

[0072] M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step one ① in step one ③;

[0073] The ratio of the volume of dimethyl sulfoxide to the amount of substance of M2 in step one ③ is (50-100) mL: 10 mmol;

[0074] The ratio of cesium fluoride to the amount of substance of M2 in step one ③ is 4.8:1;

[0075] The ratio of p-fluoronitrobenzene to the amount of substance of M2 in step one ③ is 4.8:1;

[0076] ④, N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)-4-(4-(4-methylpiperazine-1-yl)phenyl)phenyl-1,4-diamine, also named as M4, the specific preparation method is the same as step one ②, with several differences as follows:

[0077] M3 is used to replace M1 in step one ② in step one ③;

[0078] The ratio of the volume of anhydrous ethanol to the amount of substance of M3 in step one ④ is (150-200) mL: 5 mmol;

[0079] The ratio of the mass of Pd / C to the amount of substance of M3 in step one ④ is (2-2.4) g: 5 mmol;

[0080] II. Preparation of hyperbranched polyamide containing methylpiperazine and polytriphenylamine structure:

[0081] The N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazin-1-yl)phenyl)phenyl-1,4-diamine (M4), diacid monomer, triphenyl phosphite, CaCl2, pyridine and N-methyl pyrrolidone are mixed, then stirred at 130°C for 4 hours, after cooling to room temperature, poured into methanol, the precipitate is collected by filtration, washed thoroughly with methanol, and finally Soxhlet extracted with methanol to obtain hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure;

[0082] The mass ratio of M4 to diacid monomer in step two is 1:2;

[0083] The volume ratio of triphenyl phosphite to M4 in step two is 1.5 mL: 1 mmol;

[0084] The volume ratio of pyridine to M4 in step two is 1.5 mL: 1 mmol;

[0085] The volume ratio of N-methyl pyrrolidone to M4 in step two is 3 mL: 1 mmol;

[0086] The mass ratio of CaCl2 to N-methyl pyrrolidone in step two is 0.3 g: 6 mL;

[0087] The volume ratio of methanol to M4 in step two is 350 mL: 1 mmol.

[0088] Specific embodiment three: the hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure in this embodiment is applied in electrochromism as an electrochromic layer in an electrochromic device.

[0089] Specific embodiment four: the difference between this embodiment and specific embodiment three is that the application of the hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure in electrochromism as an electrochromic layer in an electrochromic device is carried out according to the following steps:

[0090] The hyperbranched polyamide containing methyl piperazine and polytriphenylamine structure is applied in electrochromism as an electrochromic layer in an electrochromic device, the electrochromic layer is coated on a conductive substrate to prepare the electrochromic device, and the electrochromic layer produces electrochromism under the action of an applied electric field. Other steps and parameters are the same as those in specific embodiment four.

[0091] Specific embodiment five: the difference between this embodiment and specific embodiment three or four is that the conductive substrate is a conductive glass or an ITO conductive resin film or a transparent silver nanowire or a transparent carbon nanotube electrode. Other steps and parameters are the same as those in specific embodiment three or four.

[0092] Sixth embodiment: the added electrolyte is a solution or gel containing lithium ions or t-butyl ammonium ions

[0093] Seventh embodiment: the voltage of the applied electric field is 0V-2.50V. Other steps and parameters are the same as those in the third to sixth embodiments.

[0094] The beneficial effects of the present application are verified by the following examples:

[0095] Example 1: the structural formula of hyperbranched polyamide P1 containing methylpiperazine and polytriphenylamine structure is as follows:

[0096]

[0097] , wherein the branching degree is 0.70.

[0098] I. Synthesis of N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazin-1-yl)phenyl)phenyl-1,4-diamine monomer:

[0099] ①, under N2 atmosphere, 4-(4-methylpiperazine) aniline monomer, cesium fluoride, p-fluoroniitrobenzene and dimethyl sulfoxide were placed in a three-necked flask, the system was heated to 120℃ for reflux reaction, and thin layer chromatography was used to determine the end of the reaction, then the heat source was turned off; the cooled mixture was poured into a mixed solution of deionized water and ethanol until the crude product was precipitated, filtered, and then recrystallized with methanol, filtered again, and the obtained product was vacuum dried to obtain red powder M1;

[0100] The volume ratio of dimethyl sulfoxide to 4-(4-methylpiperazine) aniline monomer in step one ① is (50-100) mL: 10 mmol;

[0101] The molar ratio of cesium fluoride to 4-(4-methylpiperazine) aniline monomer in step one ① is 2.2:1;

[0102] The molar ratio of p-fluoroniitrobenzene to 4-(4-methylpiperazine) aniline monomer in step one ① is 2.2:1;

[0103] The temperature of vacuum drying in step one ① is 45℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is -30 to -29 KPa;

[0104] (ii) Under room temperature, anhydrous ethanol, Pd / C and M1 were added into a three-neck flask and stirred; under N2, hydrazine hydrate was added into the flask by using a constant pressure funnel at a dropping speed of 1-2 drops per second; the system was heated to 80°C until the solution was refluxed, and then filtered to remove Pd / C after the reaction was completed; the filtrate was poured into brine under stirring, and extracted with dichloromethane solvent for 3 times; the obtained organic phase solution was dried with anhydrous magnesium sulfate to remove water, and then filtered to obtain a transparent solution; the filtrate was rotary evaporated, and then vacuum dried to obtain a grayish white monomer M2;

[0105] In step (ii) of the first step, the volume ratio of anhydrous ethanol to the amount of substance of M1 is (150-200) mL: 10 mmol;

[0106] In step (ii) of the first step, the mass ratio of Pd / C to the amount of substance of M1 is (1-1.2) g: 5 mmol;

[0107] In step (ii) of the first step, the volume ratio of hydrazine hydrate to the amount of substance of M1 is 2.5 mL: 1 mmol;

[0108] In step (ii) of the first step, the Pd / C is a C-doped composite material of Pd, and the mass fraction of Pd in Pd / C is 5%;

[0109] In step (ii) of the first step, the temperature of vacuum drying is 30°C, the time of vacuum drying is 48-64 hours, and the pressure of vacuum drying is -30 to -29 KPa;

[0110] (iii) The specific preparation method of M3 is the same as that of step (i) 1, with several differences as follows:

[0111] In step (iii) of the first step, M2 is used to replace the raw material 4-(4-methylpiperazine) aniline monomer in step (i) 1;

[0112] In step (iii) of the first step, the volume ratio of dimethyl sulfoxide to the amount of substance of M2 is (50-100) mL: 10 mmol;

[0113] In step (iii) of the first step, the amount of substance ratio of cesium fluoride to M2 is 4.8: 1;

[0114] In step (iii) of the first step, the amount of substance ratio of p-fluoroniitrobenzene to M2 is 4.8: 1;

[0115] (iv) N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)-4-(4-(4-methylpiperazine-1-yl)phenyl)phenyl-1,4-diamine, also named as M4, the specific preparation method of which is the same as that of step (ii) of the first step, with several differences as follows:

[0116] In step (iv) of the first step, M3 is used to replace M1 in step (ii) of the first step;

[0117] The ratio of the volume of anhydrous ethanol to the amount of substance of M3 in step one ④ is (150-200) mL: 5 mmol;

[0118] The ratio of the mass of Pd / C to the amount of substance of M3 in step one ④ is (2-2.4) g: 5 mmol;

[0119] II. Preparation of hyperbranched polyamide containing methyl piperazine and polytriphene structure:

[0120] N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazin-1-yl)phenyl)phenyl-1,4-diamine (M4), diacid monomer, triphenyl phosphite, CaCl2, pyridine and N-methyl pyrrolidone were mixed, then stirred at 130℃ for 4 hours, after cooling to room temperature, poured into methanol, the precipitate was collected by filtration, washed thoroughly with methanol, and finally Soxhlet extracted with methanol to obtain hyperbranched polyamide containing methyl piperazine and polytriphene structure;

[0121] The ratio of the amount of substance of M4 to diacid monomer in step two is 1:2;

[0122] The ratio of the volume of triphenyl phosphite to the amount of substance of M4 in step two is 1.5 mL: 1 mmol;

[0123] The ratio of the volume of pyridine to the amount of substance of M4 in step two is 1.5 mL: 1 mmol;

[0124] The ratio of the volume of N-methyl pyrrolidone to the amount of substance of M4 in step two is 3 mL: 1 mmol;

[0125] The ratio of the mass of CaCl2 to the volume of N-methyl pyrrolidone in step two is 0.3 g: 6 mL;

[0126] The ratio of the volume of methanol to the amount of substance of M4 in step two is 350 mL: 1 mmol.

[0127] Examples two to four: the structural formula of hyperbranched polyamide P2-P4 containing methyl piperazine and polytriphene structure is similar to P1.

[0128] The specific preparation method of P2 is the same as that of P1 in example one, except that in example two, 4,4'-diphenyl sulfone dicarboxylic acid is used instead of 1,4-cyclohexane dicarboxylic acid, and the branching degree is 0.87.

[0129] The specific preparation method of P3 is the same as that of P1 in example one, except that in example three, 4,4'-dicarboxy diphenyl ether is used instead of 1,4-cyclohexane dicarboxylic acid, and the branching degree is 0.50.

[0130] P4 The preparation method is the same as P1 in Example 1, except that 2,2-bis(4- carboxyphenyl)hexafluoropropane is used as raw material 2,2-bis(4-carboxyphenyl)hexafluoropropane instead of 1,4-cyclohexanedicarboxylic acid in Example 4, wherein the branching degree is 0.81.

[0131] Figure 1 The hydrogen nuclear magnetic resonance spectrum of N1,N1-bis(4- aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazin-1-yl) phenyl)phenyl-1,4-diamine monomer (M4) prepared in Example 1; it is shown that N1,N1-bis(4- aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl)4-(4-(4-methylpiperazin-1-yl) phenyl)phenyl-1,4-diamine monomer (M4) is synthesized in Example 1;

[0132] Figure 2 The Fourier infrared spectra of the four kinds of hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples 1 to 4; it is shown that Figure 2 the four kinds of hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples 1 to 4 have the same characteristic absorption peaks, and the characteristic absorption peaks are 3299~3240cm Figure 2 -1; -1 the characteristic absorption peak of -NH- in amide bond, 1663cm -1 the characteristic absorption peak of carbonyl in amide bond, 1256cm -1 the characteristic absorption peak of N-C in amide bond; it is shown that the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure are synthesized in Example 2;

[0133] Figure 3 The cyclic voltammograms of the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples 1 to 4; it is shown that Figure 3 the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples 1 to 4 have the same characteristic absorption peaks, and the characteristic absorption peaks are 3299~3240cm -1; it is shown that the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples 1 to 4 undergo redox reactions under the condition of applied voltage, and the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure will produce color changes in the redox process; it is shown that the hyperbranched polyamides containing methyl piperazine and multi-triphenylamine structure prepared in Examples 1 to 4 have electrochromic properties;

[0134] Figure 4 Thermogravimetric analysis spectra of hyperbranched polyamides containing methylpiperazine and polytriazene structure prepared in Example 1 to 4; from Figure 4 It can be seen that the weight loss of hyperbranched polyamides containing methylpiperazine and polytriazene structure is 10% in nitrogen atmosphere, and the thermal decomposition temperature range is 422-458℃, indicating that these polymers have good thermodynamic stability. When the temperature is heated to 800℃, the carbon residue rate of the polymer is greater than 47%. This is because the polymer has a high content of aromatic structure, which can indicate that the polymer has good thermal stability and can work in a high temperature environment;

[0135] Figure 5 The electrochromic spectra of hyperbranched polyamides containing methylpiperazine and polytriazene structure prepared in Example 1 to 4; the electrochromic properties are determined by testing the change of absorbance in the ultraviolet-visible-near infrared absorption spectrum with the applied voltage. Taking the electrochromic properties of P1 as an example, as the voltage gradually increases, the absorption peak at 336nm gradually decreases, the absorption peaks at 445nm and 1166nm gradually increase, and the P1 film changes from colorless to yellow-green; when the voltage increases to 0.9V, the absorption peak at 445nm gradually decreases, the absorption peak at 1166nm rises to the maximum, a new absorption peak appears at 643nm, and the P1 film changes to light blue; when the potential increases to 1.3V to achieve complete oxidation, the absorption peak at 1166nm gradually decreases, and a new absorption peak appears at 867nm, and the film turns into dark blue;

[0136] Figure 6 The dynamic curve of transmittance of hyperbranched polyamide P1 film containing methylpiperazine and polytriazene structure prepared in Example 1 at 0.0V-0.9V and 1166nm wavelength with time; from Figure 6 It can be seen that the optical contrast of P1 is 77%, and after 1800 cycles, the optical contrast basically does not change, indicating that the polymer P1 has excellent optical contrast.

[0137] Figure 7 The principle diagram of electrochromic device prepared by hyperbranched polyamide P1 film containing methylpiperazine and polytriazene structure prepared in Example 1, P1 film as electrochromic layer, conductive layer as conductive glass or ITO tube electrode, and electrolyte as solution or gel containing lithium ion or tert-butyl ammonium ion.

Claims

1. N1,N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl) 4-(4-(4-methylpiperazin-1-yl)phenyl)phenyl-1,4-diamine monomer characterized in that, The monomer structure is as follows:

2. Hyperbranched polyamide containing methylpiperazine and polytriphenylamine structures, characterized in that, The hyperbranched polyamide structure is as follows: The branching degree is 0.50-0.

81.

3. The method for preparing hyperbranched polyamide according to claim 2, characterized in that, Comprising the following steps: I. Synthesis of N1, N1-bis (4-aminophenyl) -N4- (4- (bis (4-aminophenyl amino) phenyl) 4- (4- (4-methyl piperazine) phenyl) phenyl-1, 4-diamine monomer: ①, under N2 atmosphere, 4- (4-methyl piperazine) aniline monomer, cesium fluoride, p-fluoroniobenzene and dimethyl sulfoxide were placed in a three-necked flask, the system was heated to 120℃ and refluxed, and the reaction was judged by thin layer chromatography after the reaction was completed. Turn off the heat source; pour the cooled mixture into a mixture of deionized water and ethanol solution until the crude product is precipitated, filter, recrystallize the crude product with methanol, filter again, and vacuum dry the obtained product to obtain red powder M1; The volume ratio of dimethyl sulfoxide to 4- (4-methyl piperazine) aniline monomer in step 1 ① is (50-100) mL: 10 mmol; The mass ratio of cesium fluoride to 4- (4-methyl piperazine) aniline monomer in step 1 ① is 2.2:1; The molar ratio of p-fluoroniobenzene to 4- (4-methyl piperazine) aniline monomer in step 1 ① is 2.2:1; The temperature of vacuum drying in step 1 ① is 45℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 to-29 KPa; ②, under room temperature conditions, anhydrous ethanol, Pd / C and M1 were added to a three-necked flask and stirred; under N2 conditions, hydrazine hydrate was added to the three-necked flask at a drop rate of 1-2 drops per second using a constant pressure funnel; the system was heated to 80℃ to reflux the solution, and after the reaction was completed, the Pd / C was removed by hot filtration, and the filtrate was poured into salt water under stirring, extracted with dichloromethane solvent for 3 times; The obtained organic phase solution was dried by anhydrous magnesium sulfate, filtered to obtain a transparent solution; the filtrate was rotary evaporated and vacuum dried to obtain a grayish white monomer M2; The volume ratio of anhydrous ethanol to M1 in step 1 ② is (150-200) mL: 10 mmol; The mass ratio of Pd / C to M1 in step 1 ② is (1-1.2) g: 5 mmol; The volume ratio of hydrazine hydrate to M1 in step 1 ② is 2.5 mL: 1 mmol; The Pd / C in step 1 ② is a C-doped composite material of Pd, and the mass fraction of Pd in Pd / C is 5%; The temperature of vacuum drying in step 1 ② is 30℃, the time of vacuum drying is 48-64 hours, and the pressure of vacuum drying is-30 to-29 KPa; ③, the specific preparation method of M3 is the same as step 1 ①, with the following differences: M2 is used instead of 4- (4-methyl piperazine) aniline monomer in step 1 ① in step 1 ③; The volume ratio of dimethyl sulfoxide to M2 in step 1 ③ is (50-100) mL: 10 mmol; The mass ratio of cesium fluoride to M2 in step 1 ③ is 4.8:1; The molar ratio of p-fluoroniobenzene to M2 in step 1 ③ is 2.2:1; The temperature of vacuum drying in step 1 ③ is 45℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 to-29 KPa; The molar ratio of p-fluoronitrobenzene to M2 in step one ③ is 4.8:1; ④, N1, N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl) 4-(4-(4-methylpiperazine-1-yl) phenyl) phenyl-1,4-diamine, also named as M4, the specific preparation method is the same as step one ②, with several differences as follows: M3 is used in step one ④ instead of M1 in step one ②; The volume of anhydrous ethanol to the molar amount of M3 in step one ④ is (150-200) mL:5 mmol; The mass of Pd / C to the molar amount of M3 in step one ④ is (2-2.4) g:5 mmol; II. Preparation of hyperbranched polyamide containing methylpiperazine and polytriphene structure: Mix N1, N1-bis(4-aminophenyl)-N4-(4-(bis(4-aminophenylamino)phenyl) 4-(4-(4-methylpiperazine-1-yl) phenyl) phenyl-1,4-diamine (M4), diacid monomer, triphenyl phosphite, CaCl2, pyridine and N-methyl pyrrolidone, then stir at 130℃ for 4 hours, pour into methanol after cooling to room temperature, collect the precipitate by filtration, wash thoroughly with methanol, and finally perform Soxhlet extraction with methanol to obtain hyperbranched polyamide containing methylpiperazine and polytriphene structure; The molar ratio of M4 to diacid monomer in step two is 1:2; The volume of triphenyl phosphite to the molar amount of M4 in step two is 1.5 mL:1 mmol; The volume of pyridine to the molar amount of M4 in step two is 1.5 mL:1 mmol; The volume of N-methyl pyrrolidone to the molar amount of M4 in step two is 3 mL:1 mmol; The mass of CaCl2 to the volume of N-methyl pyrrolidone in step two is 0.3 g:6 mL; The volume of methanol to the molar amount of M4 in step two is 350 mL:1 mmol.

4. The method of claim 3, wherein the hyperbranched polyamide is prepared by the reaction of a polyfunctional amine and a polyfunctional carboxylic acid in the presence of a catalyst. 5 The diacid monomers in step two are 1,4-cyclohexane dicarboxylic acid, 4,4-diphenylsulfonyl dicarboxylic acid, 4,4'-dicarboxy diphenyl ether and 2,2-bis(4-carboxyphenyl) hexafluoropropane, and the prepared polymers are P1, P2, P3 and P4 respectively.

5. The method of claim 3, wherein the hyperbranched polyamide is prepared by the reaction of a polyfunctional amine and a polyfunctional carboxylic acid in the presence of a catalyst. The methanol used for Soxhlet extraction in step two is 300 mL, and the time is 72 hours.

6. Application of hyperbranched polyamide containing methylpiperazine and polytriphene structure in electrochromism as electrochromic layer in electrochromic device.

7. Use according to claim 6, characterized in that, The application of hyperbranched polyamide containing methylpiperazine and polytriphene structure as electrochromic layer in electrochromic device in smart windows and displays is carried out according to the following steps: The hyperbranched polyamide containing methylpiperazine and polytriphene structure is coated on a conductive substrate as an electrochromic layer, an electrolyte solution is added between two electrodes to prepare an electrochromic device; the electrochromic device produces color change behavior under the action of an external electric field.

8. Use according to claim 7, characterized in that, The conductive substrate is ITO conductive glass or ITO conductive resin film or transparent silver nanowire or transparent carbon nanotube electrode.

9. Use according to claim 7, characterized in that, The added electrolyte is a solution or gel containing lithium ions or t-butylammonium ions.

10. Use according to claim 7, characterized in that, The voltage of the applied electric field is 0-2.5 V.

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