CN110922586B - Polyamide containing triarylamine with isopropyl directly bonded with nitrogen atom, and preparation method and application thereof - Google Patents
Polyamide containing triarylamine with isopropyl directly bonded with nitrogen atom, and preparation method and application thereof Download PDFInfo
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- CN110922586B CN110922586B CN201911340959.9A CN201911340959A CN110922586B CN 110922586 B CN110922586 B CN 110922586B CN 201911340959 A CN201911340959 A CN 201911340959A CN 110922586 B CN110922586 B CN 110922586B
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- isopropyl
- triarylamine
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- 125000004433 nitrogen atom Chemical group N* 0.000 title claims abstract description 159
- 125000005259 triarylamine group Chemical group 0.000 title claims abstract description 158
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 title claims abstract description 154
- 239000004952 Polyamide Substances 0.000 title claims abstract description 117
- 229920002647 polyamide Polymers 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 115
- 239000000178 monomer Substances 0.000 claims description 106
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- 238000001291 vacuum drying Methods 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 43
- VRKQEIXDEZVPSY-UHFFFAOYSA-N 4-n-phenyl-4-n-propan-2-ylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(C(C)C)C1=CC=CC=C1 VRKQEIXDEZVPSY-UHFFFAOYSA-N 0.000 claims description 40
- 239000011449 brick Substances 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 40
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000012043 crude product Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 21
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 16
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 claims description 16
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 16
- 239000012312 sodium hydride Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004809 thin layer chromatography Methods 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- YRCBWGJIQJYWQC-UHFFFAOYSA-N 4-N-[4-(4-amino-N-propan-2-ylanilino)phenyl]-4-N-phenylbenzene-1,4-diamine Chemical compound NC1=CC=C(C=C1)N(C1=CC=C(C=C1)N(C1=CC=CC=C1)C1=CC=C(C=C1)N)C(C)C YRCBWGJIQJYWQC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 229920000547 conjugated polymer Polymers 0.000 abstract description 5
- 239000002798 polar solvent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 description 30
- 230000008859 change Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- -1 triarylamine compound Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- SQJQLYOMPSJVQS-UHFFFAOYSA-N 4-(4-carboxyphenyl)sulfonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C=C1 SQJQLYOMPSJVQS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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Abstract
The invention relates to polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms, a preparation method and application thereof, in particular to polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms, a preparation method and application thereof, aiming at solving the problem that the existing polyamide has strong rigidity and poor solubility, so that the existing polyamide is not easy to be coated and processed; the polyamide conjugated polymer containing the triarylamine directly bonded by isopropyl and nitrogen atoms, which is prepared by the invention, has the advantages that the solubility of polyamide is increased due to the introduction of isopropyl, the polyamide conjugated polymer is easily soluble in a polar solvent, and 0.1-0.15 g of the polyamide conjugated polymer can be dissolved in 1 ml of polar solution; the invention is applied to the field of polyamide.
Description
Technical Field
The invention relates to a polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms, a preparation method and application thereof.
Background
Aromatic polyamides have some very good properties: stable thermal property, oxidation resistance, high mechanical strength, nonflammability, chemical corrosion resistance, good radiation resistance and the like, and has wide application in the fields of civil construction, transportation, national defense and military, aviation, electronics and the like. However, the high content of benzene ring in the molecular structure of polyamide gives the polyamide chain strong rigidity, and the hydrogen bonding between molecules makes the solubility and processability of polyamide polymer not ideal, thereby limiting its application range.
Disclosure of Invention
The invention aims to solve the problem that the existing polyamide has strong rigidity and poor solubility, so that the coating processing is not easy to realize, and provides the polyamide containing the triarylamine with isopropyl directly bonded with nitrogen atoms, and the preparation method and the application thereof.
The polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms is polyamide P1 containing triarylamine with isopropyl directly bonded with nitrogen atoms, polyamide P2 containing triarylamine with isopropyl directly bonded with nitrogen atoms, polyamide P3 containing triarylamine with isopropyl directly bonded with nitrogen atoms, polyamide P4 containing triarylamine with isopropyl directly bonded with nitrogen atoms or polyamide P5 containing triarylamine with isopropyl directly bonded with nitrogen atoms;
the structural formula of the triarylamine polyamide P1 containing isopropyl groups directly bonded to nitrogen atoms is as follows:
the polyamide P2 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P3 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P4 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P5 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
wherein n is an integer of 12 to 21.
The preparation method of the triarylamine polyamide containing isopropyl and nitrogen atoms directly bonded comprises the following steps:
one, synthesis of N1，N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
at N2Under the atmosphere, placing an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene at a dropping speed of 1-2 drops per second, heating to 115 ℃, carrying out condensation reflux, and cooling after the constant temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product for 2-3 times, then recrystallizing by using ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
wherein the molar volume ratio of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer to the anhydrous N, N-dimethylformamide is 10 mmol: (100-150) mL;
the mass ratio of sodium hydride to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the molar ratio of the p-fluoronitrobenzene to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the molar volume ratio of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer to cold water is 10 mmol: (400-450) mL;
the temperature of the vacuum drying is 80 ℃, the time of the vacuum drying is 36-48 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
② adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-neck flask at room temperature, and introducing N into the three-neck flask2Dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating until the solution is refluxed, stopping heating after the reflux reaction is finished, filtering at 79-80 ℃ to remove Pd/C, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering out the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
wherein the molar volume ratio of the brick red powder M1 to absolute ethyl alcohol is 10 mmol: (100-120) mL;
the mass ratio of the Pd/C to the amount of brick red powder M1 is (1-1.2) g: 5mmol of the active carbon;
the heating speed is 9-10 ℃ per minute when the temperature is raised until the solution flows back;
the molar volume ratio of the brick red powder M1 to hydrazine hydrate is 3 mL: 1mmol of the active component;
the volume ratio of the filtrate to the cold water is 1: (3-4);
the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
the temperature of the vacuum drying is 28 ℃, the time of the vacuum drying is 48-60 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
secondly, preparing the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms:
triarylamine monomer with isopropyl directly bonded with nitrogen atom, diacid monomer, triphenyl phosphite, CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
wherein the mass ratio of the triarylamine monomer and the diacid monomer, in which the isopropyl group is directly bonded to the nitrogen atom, is 1: 1;
the molar volume ratio of the triarylamine monomer directly bonded with the propyl group and the nitrogen atom to triphenyl phosphite is 1 mmol: 1.2 mL;
the molar volume ratio of the isopropyl group to the nitrogen atom directly bonded triarylamine monomer to pyridine is 1 mmol: 0.6 mL;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the N-methyl pyrrolidone is 1 mmol: 1.5 mL;
the CaCl is2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the methanol is 1 mmol: (200-250) mL.
The invention relates to the use of polyamides containing triarylamines having isopropyl groups directly bonded to nitrogen atoms as electrochromic layers in electrochromic devices.
The invention aims to prepare the polyamide with good electrochromic capability, the service strength and the service life of the film are enhanced by designing the polyamide containing triarylamine to have a stable molecular structure, meanwhile, the problem of reduced solubility caused by the increase of the rigidity of a molecular structure is solved, the existing polyamide has the problems of strong rigidity and unsatisfactory solubility and processability, but has good oxidation resistance and chemical corrosion resistance, can enhance the service strength and the service life of the film, the direct connection of N atom to isopropyl group in triarylamine can make electrochromic polymer have good solubility, convenient coating processing, and synthesize two advantages, the preparation of triarylamine polyamide containing isopropyl group directly bonded with nitrogen atom has good oxidation resistance, chemical corrosion resistance, good solubility and film-forming property, also provides polyamide containing triarylamine with isopropyl directly bonded with nitrogen atom, and its preparation method and application.
The invention has the beneficial effects that:
the triarylamine compound is a non-planar molecular configuration, and a central nitrogen atom loses lone pair electrons under the action of an electric field to form an ion free radical to provide electrons. Because the steric hindrance of the benzene ring is larger, the super-electron conjugation effect is stronger, and the stability of the free radical is higher. The free radical characteristics enable triphenylamine and derivatives thereof to have good transmission performance and higher hole mobility. The triarylamine polyamide polymer containing isopropyl and nitrogen atom directly bonded has obviously improved solubility, more obvious color change and high contrast due to the existence of isopropyl. Therefore, the prepared polyamide conjugated polymer containing triarylamine with isopropyl directly bonded with nitrogen atoms has improved solubility of polyamide due to the introduction of isopropyl, is easily soluble in a polar solvent, and can be dissolved in 0.35-0.45 g per 1 ml of polar solution;
secondly, the polymer has excellent electrochromic property;
electrochromism refers to a phenomenon in which a substance undergoes an electrochemical redox reaction to cause color change under the drive of an external voltage or current. The polyamide polymer containing triarylamine having isopropyl group directly bonded to nitrogen atom contains active sites for electron transport and electron transition, and when a certain voltage is applied to the polymer, electron transition occurs inside the polymer to cause color change. The polymer has obvious color change within the voltage range of 0.50-1.6V, and the coloring time of the polymer is 5.0-6.0 s; bleaching for 5.0-5.7 s; the color is blue when coloring, the color is nearly colorless when bleaching, and the contrast is higher when electrochromism is carried out.
Drawings
FIG. 1 shows N prepared in example one1，N4-bis (4-aminophenyl) -N1-isopropyl-N4-C-H nuclear magnetic spectrum of phenyl-1, 4-diamine monomer;
FIG. 2 shows the preparation of a polyamide polymer P1 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, prepared in example one1H nuclear magnetic spectrum;
FIG. 3 shows the preparation of a polyamide polymer P2 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, prepared in example two1H nucleusA magnetic spectrum;
FIG. 4 shows a modification of the polyamide polymer P3 of example III, which polyamide polymer contains a triarylamine having isopropyl groups directly bonded to the nitrogen atom1H nuclear magnetic spectrum;
FIG. 5 is a depiction of a polyamide polymer P4 prepared as described in example four and containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom1H nuclear magnetic spectrum;
FIG. 6 shows the preparation of a polyamide polymer P5 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, prepared in example five1H nuclear magnetic spectrum;
FIG. 7 is a cyclic voltammogram of five polyamide polymers containing triarylamines having isopropyl groups directly bonded to the nitrogen atom prepared in examples one to five; wherein a is P1, b is P2, c is P3, d is P4, e is P5;
FIG. 8 is an electrochromic diagram of a polyamide polymer P1 which was prepared according to example one and contains triarylamine having isopropyl groups bonded directly to the nitrogen atom;
FIG. 9 is the electrochromic diagram of a polyamide polymer P2 prepared in example two and containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom;
FIG. 10 is the electrochromic diagram of a polyamide polymer P3 prepared in example III and containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom;
FIG. 11 is the electrochromic diagram of a polyamide polymer P4 prepared in example IV and containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom;
FIG. 12 is the electrochromic diagram of a polyamide polymer P5 prepared in example V and containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom;
FIG. 13 is a graph of the thermogravimetric plot of five polyamide polymers containing triarylamines having isopropyl groups directly bonded to nitrogen atoms prepared in examples one to five; wherein a is P1, b is P2, c is P3, d is P4, and e is P5.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the polyamide containing triarylamine in which isopropyl group is directly bonded to nitrogen atom in this embodiment is polyamide P1 containing triarylamine in which isopropyl group is directly bonded to nitrogen atom, polyamide P2 containing triarylamine in which isopropyl group is directly bonded to nitrogen atom, polyamide P3 containing triarylamine in which isopropyl group is directly bonded to nitrogen atom, polyamide P4 containing triarylamine in which isopropyl group is directly bonded to nitrogen atom, or polyamide P5 containing triarylamine in which isopropyl group is directly bonded to nitrogen atom;
the structural formula of the triarylamine polyamide P1 containing isopropyl groups directly bonded to nitrogen atoms is as follows:
the polyamide P2 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P3 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P4 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P5 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
The beneficial effects of the embodiment are as follows:
the triarylamine compound is a non-planar molecular configuration, and a central nitrogen atom loses lone pair electrons under the action of an electric field to form an ion free radical to provide electrons. Because the steric hindrance of the benzene ring is larger, the super-electron conjugation effect is stronger, and the stability of the free radical is higher. The free radical characteristics enable triphenylamine and derivatives thereof to have good transmission performance and higher hole mobility. In the polyamide polymer containing triarylamine in which isopropyl group is directly bonded to nitrogen atom in this embodiment, the presence of isopropyl group significantly improves the solubility of the polymer, makes the discoloration more noticeable, and improves the contrast. Therefore, the polyamide conjugated polymer containing triarylamine with isopropyl directly bonded with nitrogen atoms, prepared by the embodiment, has improved solubility of polyamide due to the introduction of isopropyl, is easily soluble in a polar solvent, and can be dissolved in 0.35-0.4 g of polar solution per 1 ml;
secondly, the polymer of the embodiment has excellent electrochromic performance;
electrochromism refers to a phenomenon in which a substance undergoes an electrochemical redox reaction to cause color change under the drive of an external voltage or current. The polyamide polymer containing triarylamine having isopropyl group directly bonded to nitrogen atom contains active sites for electron transport and electron transition, and when a certain voltage is applied to the polymer, electron transition occurs inside the polymer to cause color change. The polymer of the embodiment has obvious color change within the voltage range of 0.50-1.6V, and the coloring time of the polymer of the embodiment is 5.0-6.0 s; bleaching for 5.0-5.7 s; the color is blue when coloring, the color is nearly colorless when bleaching, and the contrast is higher when electrochromism is carried out.
The second embodiment is as follows: the preparation process of the triarylamine-containing polyamide having isopropyl groups directly bonded to nitrogen atoms according to this embodiment is carried out by the following steps:
one, synthesis of N1，N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl-1, 4-diamine monoBody:
at N2Under the atmosphere, placing an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene at a dropping speed of 1-2 drops per second, heating to 115 ℃, carrying out condensation reflux, and cooling after the constant temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product for 2-3 times, then recrystallizing by using ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
wherein the molar volume ratio of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer to the anhydrous N, N-dimethylformamide is 10 mmol: (100-150) mL;
the mass ratio of sodium hydride to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the molar ratio of the p-fluoronitrobenzene to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the molar volume ratio of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer to cold water is 10 mmol: (400-450) mL;
the temperature of the vacuum drying is 80 ℃, the time of the vacuum drying is 36-48 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
② adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-neck flask at room temperature, and introducing N into the three-neck flask2Dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating until the solution is refluxed, stopping heating after the reflux reaction is finished, filtering at 79-80 ℃ to remove Pd/C, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering out the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
wherein the molar volume ratio of the brick red powder M1 to absolute ethyl alcohol is 10 mmol: (100-120) mL;
the mass ratio of the Pd/C to the amount of brick red powder M1 is (1-1.2) g: 5mmol of the active carbon;
the heating speed is 9-10 ℃ per minute when the temperature is raised until the solution flows back;
the molar volume ratio of the brick red powder M1 to hydrazine hydrate is 3 mL: 1mmol of the active component;
the volume ratio of the filtrate to the cold water is 1: (3-4);
the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
the temperature of the vacuum drying is 28 ℃, the time of the vacuum drying is 48-60 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
secondly, preparing the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms:
triarylamine monomer with isopropyl directly bonded with nitrogen atom, diacid monomer, triphenyl phosphite, CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
wherein the mass ratio of the triarylamine monomer and the diacid monomer, in which the isopropyl group is directly bonded to the nitrogen atom, is 1: 1;
the molar volume ratio of the triarylamine monomer directly bonded with the propyl group and the nitrogen atom to triphenyl phosphite is 1 mmol: 1.2 mL;
the molar volume ratio of the isopropyl group to the nitrogen atom directly bonded triarylamine monomer to pyridine is 1 mmol: 0.6 mL;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the N-methyl pyrrolidone is 1 mmol: 1.5 mL;
the CaCl is2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the methanol is 1 mmol: (200-250) mL.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: judging whether the constant-temperature reaction is finished or not by using a thin-layer chromatography, wherein a solvent used by the thin-layer chromatography is a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: (8-9). The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: and step two, judging whether the reflux reaction is finished or not by using a thin-layer chromatography, wherein a solvent used by the thin-layer chromatography is a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is 1: 4. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: this embodiment is different from one of the second to fourth embodiments in that: and in the second step, the diacid monomer is 4- (4-carboxyphenoxy) benzoic acid, terephthalic acid, 4' -dicarboxydiphenylsulfone, 1, 4-naphthalenedicarboxylic acid or 1, 4-cyclohexanedicarboxylic acid, and the polymers are respectively prepared into P1, P2, P3, P4 and P5. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the present embodiment is different from one of the second to fifth embodiments in that: in step two, 300mL of methanol was used for 72 hours. The rest is the same as one of the second to fifth embodiments.
The seventh embodiment: the present embodiment is different from one of the second to sixth embodiments in that: the temperature of the cold water is 0 ℃, and the temperature of the hot water is 99-100 ℃. The rest is the same as one of the second to sixth embodiments.
The specific implementation mode is eight: the use of polyamides containing triarylamines having isopropyl groups directly bonded to nitrogen atoms as electrochromic layers in electrochromic devices.
The specific implementation method nine: the eighth embodiment is different from the eighth embodiment in that: the application of the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms as an electrochromic layer in an electrochromic device in electrochromism is carried out according to the following steps:
the method is characterized in that the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms is used 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 generates electrochromism under the action of an external electric field. The rest is the same as the embodiment eight.
The detailed implementation mode is ten: the present embodiment differs from the embodiment eight or nine in that: the conductive substrate is conductive glass, and the voltage of an external electric field is 0-1.60V. The others are the same as the embodiments eight or nine.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the polyamide P1 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
The preparation method comprises the following steps:
firstly, synthesizing N1, N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
at N2Under the atmosphere, putting an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene into the solution at a dropping speed of 2 drops per second, heating to 115 ℃ for condensation reflux, judging whether the constant-temperature reaction is finished by using a thin-layer chromatography, and cooling after the constant-temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product with hot water for 3 times, recrystallizing the crude product washed with hot water by using ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
the ratio of the volume of the anhydrous N, N-dimethylformamide to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step (i) is 150 mL: 10 mmol;
in the first step, the mass ratio of the sodium hydride to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
in the first step, the molar ratio of p-fluoronitrobenzene to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the ratio of the volume of the cold water to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step is 450 mL: 10 mmol;
the temperature of the cold water in the first step is 0 ℃;
the temperature of the hot water in the first step is 100 ℃;
in the first step, the temperature of vacuum drying is 80 ℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 KPa;
adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-necked bottle at room temperature, introducing N2 into the three-necked bottle, and dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating until the solution is refluxed, judging whether the reflux reaction is finished or not by using a thin-layer chromatography, stopping heating after the reflux reaction is finished, filtering to remove Pd/C at 79-80 ℃, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
the ratio of the volume of the absolute ethyl alcohol to the amount of the brick red powder M1 in the first step is 120 mL: 10 mmol;
in the first step, the ratio of the mass of the Pd/C to the mass of the brick red powder M1 is 1.2 g: 5mmol of the active carbon;
in the first step, the temperature is raised to 10 ℃ per minute until the solution is refluxed;
the ratio of the volume of hydrazine hydrate to the amount of brick red powder M1 in the first step is 3 mL: 1mmol of the active component;
in the first step, the volume ratio of the filtrate to the cold water is 1: 4;
the temperature of the cold water in the first step is 0 ℃;
step one, the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
in the first step, the temperature of vacuum drying is 28 ℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 KPa;
secondly, preparation of a polyamide P1 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom:
triarylamine monomer with isopropyl directly bonded with nitrogen atom, 4- (4-carboxyphenoxy) benzoic acid, triphenyl phosphite and CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
in the second step, the mass ratio of the isopropyl group to the triarylamine monomer directly bonded with the nitrogen atom to the 4- (4-carboxyphenoxy) benzoic acid is 1: 1;
step two, the ratio of the volume of the triphenyl phosphite to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.2 mL: 1mmol of the active component;
and the ratio of the volume of the pyridine to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the step two is 0.6 mL: 1mmol of the active component;
and step two, the ratio of the volume of the N-methyl pyrrolidone to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.5 mL: 1mmol of the active component;
step two of CaCl2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the ratio of the volume of the methanol to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the second step is 250 mL: 1 mmol.
Example two: the polyamide P2 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
The preparation method comprises the following steps:
firstly, synthesizing N1, N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
placing an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle under the atmosphere of N2, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene into the solution at a dropping speed of 1-2 drops per second, heating to 115 ℃ for condensation reflux, judging whether the constant-temperature reaction is finished by using a thin-layer chromatography, and cooling after the constant-temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product with hot water for 2-3 times, recrystallizing the hot water-washed crude product with ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
the ratio of the volume of the anhydrous N, N-dimethylformamide to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step (i) is 150 mL: 10 mmol;
in the first step, the mass ratio of the sodium hydride to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
in the first step, the molar ratio of p-fluoronitrobenzene to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the ratio of the volume of the cold water to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step is 450 mL: 10 mmol;
the temperature of the cold water in the first step is 0 ℃;
the temperature of the hot water in the first step is 100 ℃;
in the first step, the temperature of vacuum drying is 80 ℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 KPa;
② adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-neck flask at room temperature, and introducing N into the three-neck flask2Dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating to reflux, and determining by thin layer chromatographyWhether the flow reaction is finished or not, stopping heating after the reflux reaction is finished, filtering at 79-80 ℃ to remove Pd/C, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering out the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
the ratio of the volume of the absolute ethyl alcohol to the amount of the brick red powder M1 in the first step is 120 mL: 10 mmol;
in the first step, the ratio of the mass of the Pd/C to the mass of the brick red powder M1 is 1.2 g: 5mmol of the active carbon;
in the first step, the temperature is raised to 10 ℃ per minute until the solution is refluxed;
the ratio of the volume of hydrazine hydrate to the amount of brick red powder M1 in the first step is 3 mL: 1mmol of the active component;
in the first step, the volume ratio of the filtrate to the cold water is 1: 4;
the temperature of the cold water in the first step is 0 ℃;
step one, the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
in the first step, the temperature of vacuum drying is 28 ℃, the time of vacuum drying is 48-60 hours, and the pressure of vacuum drying is-30 to-29 KPa;
secondly, preparation of a polyamide P2 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom:
mixing isopropyl and triarylamine monomer directly bonded with nitrogen atoms, terephthalic acid, triphenyl phosphite, CaCl2, pyridine and N-methyl pyrrolidone, stirring at 120 ℃ for 3 hours, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the final product;
in the second step, the mass ratio of the isopropyl group to the triarylamine monomer directly bonded with the nitrogen atom to the terephthalic acid is 1: 1;
step two, the ratio of the volume of the triphenyl phosphite to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.2 mL: 1mmol of the active component;
and the ratio of the volume of the pyridine to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the step two is 0.6 mL: 1mmol of the active component;
and step two, the ratio of the volume of the N-methyl pyrrolidone to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.5 mL: 1mmol of the active component;
step two of CaCl2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the ratio of the volume of the methanol to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the second step is 250 mL: 1 mmol.
Example three: the polyamide P3 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
The preparation method comprises the following steps:
firstly, synthesizing N1, N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
placing an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle under the atmosphere of N2, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene into the solution at a dropping speed of 1-2 drops per second, heating to 115 ℃ for condensation reflux, judging whether the constant-temperature reaction is finished by using a thin-layer chromatography, and cooling after the constant-temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product with hot water for 2-3 times, recrystallizing the hot water-washed crude product with ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
the ratio of the volume of the anhydrous N, N-dimethylformamide to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step (i) is 150 mL: 10 mmol;
in the first step, the mass ratio of the sodium hydride to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
in the first step, the molar ratio of p-fluoronitrobenzene to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the ratio of the volume of the cold water to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step is 450 mL: 10 mmol;
the temperature of the cold water in the first step is 0 ℃;
the temperature of the hot water in the first step is 99-100 ℃;
in the first step, the temperature of vacuum drying is 80 ℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 KPa;
adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-necked bottle at room temperature, introducing N2 into the three-necked bottle, and dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating until the solution is refluxed, judging whether the reflux reaction is finished or not by using a thin-layer chromatography, stopping heating after the reflux reaction is finished, filtering to remove Pd/C at 79-80 ℃, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
the ratio of the volume of the absolute ethyl alcohol to the amount of the brick red powder M1 in the first step is 120 mL: 10 mmol;
in the first step, the ratio of the mass of the Pd/C to the mass of the brick red powder M1 is 1.2 g: 5mmol of the active carbon;
in the first step, the temperature is raised to 10 ℃ per minute until the solution is refluxed;
the ratio of the volume of hydrazine hydrate to the amount of brick red powder M1 in the first step is 3 mL: 1mmol of the active component;
in the first step, the volume ratio of the filtrate to the cold water is 1: 4;
the temperature of the cold water in the first step is 0 ℃;
step one, the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
in the first step, the temperature of vacuum drying is 28 ℃, the time of vacuum drying is 48-60 hours, and the pressure of vacuum drying is-30 KPa;
secondly, preparation of a polyamide P3 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom:
triarylamine monomer with isopropyl directly bonded to nitrogen atom, 4' -dicarboxydiphenylsulfone, triphenyl phosphite, CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
in the second step, the mass ratio of the isopropyl group to the triarylamine monomer directly bonded with the nitrogen atom to the 4, 4' -dicarboxydiphenylsulfone is 1: 1;
step two, the ratio of the volume of the triphenyl phosphite to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.2 mL: 1mmol of the active component;
and the ratio of the volume of the pyridine to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the step two is 0.6 mL: 1mmol of the active component;
and step two, the ratio of the volume of the N-methyl pyrrolidone to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.5 mL: 1mmol of the active component;
step two of CaCl2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the ratio of the volume of the methanol to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the second step is 250 mL: 1 mmol.
Example four, a polyamide P4 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom has the following structural formula:
The preparation method comprises the following steps:
firstly, synthesizing N1, N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
placing an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle under the atmosphere of N2, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene into the solution at a dropping speed of 1-2 drops per second, heating to 115 ℃ for condensation reflux, judging whether the constant-temperature reaction is finished by using a thin-layer chromatography, and cooling after the constant-temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product with hot water for 2-3 times, recrystallizing the hot water-washed crude product with ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
the ratio of the volume of the anhydrous N, N-dimethylformamide to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step (i) is 150 mL: 10 mmol;
in the first step, the mass ratio of the sodium hydride to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
in the first step, the molar ratio of p-fluoronitrobenzene to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the ratio of the volume of the cold water to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step is 450 mL: 10 mmol;
the temperature of the cold water in the first step is 0 ℃;
the temperature of the hot water in the first step is 100 ℃;
the temperature of the vacuum drying in the first step is 80 ℃, the time of the vacuum drying is 36-48 hours, and the pressure of the vacuum drying is-30 KPa;
② adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-neck flask at room temperature, and introducing N into the three-neck flask2Using a constant pressure funnelDripping hydrazine hydrate into the mixed solution in the three-mouth bottle at the dripping speed of 2 drops per second; heating until the solution is refluxed, judging whether the reflux reaction is finished or not by using a thin-layer chromatography, stopping heating after the reflux reaction is finished, filtering to remove Pd/C at 79-80 ℃, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
the ratio of the volume of the absolute ethyl alcohol to the amount of the brick red powder M1 in the first step is 120 mL: 10 mmol;
in the first step, the ratio of the mass of the Pd/C to the mass of the brick red powder M1 is 1.2 g: 5mmol of the active carbon;
in the first step, the temperature is raised to 10 ℃ per minute until the solution is refluxed;
the ratio of the volume of hydrazine hydrate to the amount of brick red powder M1 in the first step is 3 mL: 1mmol of the active component;
in the first step, the volume ratio of the filtrate to the cold water is 1: 4;
the temperature of the cold water in the first step is 0 ℃;
step one, the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
in the first step, the temperature of vacuum drying is 28 ℃, the time of vacuum drying is 48-60 hours, and the pressure of vacuum drying is-30 KPa;
secondly, preparation of a polyamide P4 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom:
triarylamine monomer with isopropyl directly bonded with nitrogen atom, 1, 4-naphthalene dicarboxylic acid, triphenyl phosphite, CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
in the second step, the mass ratio of the isopropyl group to the triarylamine monomer directly bonded with the nitrogen atom to the 1, 4-naphthalenedicarboxylic acid is 1: 1;
step two, the ratio of the volume of the triphenyl phosphite to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.2 mL: 1mmol of the active component;
and the ratio of the volume of the pyridine to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the step two is 0.6 mL: 1mmol of the active component;
and step two, the ratio of the volume of the N-methyl pyrrolidone to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.5 mL: 1mmol of the active component;
step two of CaCl2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the ratio of the volume of the methanol to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the second step is 250 mL: 1 mmol.
Example five, a polyamide P4 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom has the following structural formula:
The preparation method comprises the following steps:
firstly, synthesizing N1, N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
at N2Under the atmosphere, placing an N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, stirring for ten minutes at 20 ℃, then adding p-fluoronitrobenzene into the solution at a dropping speed of 1-2 drops per second, heating to 115 ℃ for condensation reflux, judging whether the constant-temperature reaction is finished by using a thin-layer chromatography, and cooling after the constant-temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product with hot water for 2-3 times, recrystallizing the hot water-washed crude product with ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
the ratio of the volume of the anhydrous N, N-dimethylformamide to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step (i) is 150 mL: 10 mmol;
in the first step, the mass ratio of the sodium hydride to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
in the first step, the molar ratio of p-fluoronitrobenzene to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the ratio of the volume of the cold water to the amount of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer in the first step is 450 mL: 10 mmol;
the temperature of the cold water in the first step is 0 ℃;
the temperature of the hot water in the first step is 100 ℃;
in the first step, the temperature of vacuum drying is 80 ℃, the time of vacuum drying is 48 hours, and the pressure of vacuum drying is-30 KPa;
② adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-neck flask at room temperature, and introducing N into the three-neck flask2Dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating until the solution reflows, judging whether the reflow reaction is finished or not by using a thin-layer chromatography, stopping heating after the reflow reaction is finished, filtering at 80 ℃ to remove Pd/C, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering the solid, washing the solid with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
the ratio of the volume of the absolute ethyl alcohol to the amount of the brick red powder M1 in the first step is 120 mL: 10 mmol;
in the first step, the ratio of the mass of the Pd/C to the mass of the brick red powder M1 is 1.2 g: 5mmol of the active carbon;
in the first step, the temperature is raised to 9-10 ℃ per minute at the temperature raising speed when the solution is heated to reflux;
the ratio of the volume of hydrazine hydrate to the amount of brick red powder M1 in the first step is 3 mL: 1mmol of the active component;
in the first step, the volume ratio of the filtrate to the cold water is 1: 4;
the temperature of the cold water in the first step is 0 ℃;
step one, the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
in the first step, the temperature of vacuum drying is 28 ℃, the time of vacuum drying is 48-60 hours, and the pressure of vacuum drying is-30 KPa;
secondly, preparation of a polyamide P5 containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom:
triarylamine monomer with isopropyl directly bonded with nitrogen atom, 1, 4-cyclohexane dicarboxylic acid, triphenyl phosphite, CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
in the second step, the mass ratio of the isopropyl group to the triarylamine monomer directly bonded with the nitrogen atom to the 4- (4-carboxyphenoxy) benzoic acid is 1: 1;
step two, the ratio of the volume of the triphenyl phosphite to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.2 mL: 1mmol of the active component;
and the ratio of the volume of the pyridine to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the step two is 0.6 mL: 1mmol of the active component;
and step two, the ratio of the volume of the N-methyl pyrrolidone to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom is 1.5 mL: 1mmol of the active component;
step two of CaCl2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the ratio of the volume of the methanol to the amount of the substance of the triarylamine monomer with the isopropyl group directly bonded with the nitrogen atom in the second step is 250 mL: 1 mmol.
The polyamide polymer containing triarylamine with isopropyl directly bonded to nitrogen atom prepared in the first to fifth examples is easily soluble in polar solvent, and is soluble in 0.35-0.4 g per 1 ml of polar solution.
FIG. 1 shows N prepared in example one1，N4-bis (4-aminophenyl) -N1-isopropyl-N4-C-H nuclear magnetic spectrum of phenyl-1, 4-diamine monomer; illustrative example I Synthesis of N1，N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer.
FIGS. 2-6 are hydrogen nuclear magnetic spectra of polyamide polymers containing triarylamines having isopropyl groups directly bonded to nitrogen atoms prepared in examples one to five; as can be seen from FIGS. 2 to 6, chemical shifts δ of 6.55 to 7.84ppm in FIGS. 2 to 6, i.e., chemical shifts of H on the benzene ring, and chemical shifts δ of 9.73 to 10.67, i.e., chemical shifts of H on the amide group, illustrate that examples synthesize polyamide polymers containing triarylamine having isopropyl group directly bonded to nitrogen atom;
FIG. 7 is a cyclic voltammogram of a polyamide polymer containing a triarylamine having an isopropyl group directly bonded to a nitrogen atom prepared in example one; as can be seen from FIG. 7, P1 showed an oxidation peak at 0.79V and a reduction peak at 0.91V; p2 showed an oxidation peak at 0.78V and a reduction peak at 0.90V; p3 showed an oxidation peak at 0.72V and a reduction peak at 0.95V; p4 showed an oxidation peak at 0.77V and a reduction peak at 0.93V; p5 showed an oxidation peak at 0.77V and a reduction peak at 0.95V; the description 7 shows that the polyamide polymer containing triarylamine in which propyl groups are directly bonded to nitrogen atoms undergoes redox reaction under the condition of applied voltage, and the polyamide containing triarylamine in which propyl groups are directly bonded to nitrogen atoms undergoes color change during redox reaction. Meanwhile, due to the characteristics of the polyamide, the polymer has good chemical stability, so that the polymer film still does not fall off and still well adheres to the ITO glass sheet when the cyclic voltammetry cycle reaches more than 500 times;
FIGS. 8 to 12 are the electrochromic diagrams of polyamide polymers containing triarylamines having the propyl group directly bonded to the nitrogen atom, prepared by way of example; the electrochromic properties of PAs are determined by the optical change in the uv-vis-nir spectrum with increasing applied potential. Taking the electrochromic properties of PA-5 as an example, the absorption at 760nm intensity increases sharply with increasing potential and the color of the film changes from colorless to blue. When the applied voltage reaches 0.5V, the absorption of PA-5 starts to increase. When a voltage of 1.6V was applied, the absorption of PA-5 was maximized and the film was blue in color. After increasing the oxidation potential above 1.6V, the peak absorption at 760nm did not change, indicating complete oxidation of TPA to TPA +.
FIG. 13 is a graph of the thermogravimetric plot of polyamide polymers containing triarylamines having propyl groups directly bonded to the nitrogen atom prepared in examples one to five; as can be seen from FIG. 13, the polyamide polymer containing triarylamine having propyl groups directly bonded to nitrogen atoms began to lose a large amount of weight at about 300 ℃ and had a carbon residue of 95% at 298 to 376 ℃; when the temperature is 372-469 ℃, the residual carbon content is 90%; when the temperature is 426-586 ℃, the residual carbon content is 80%; when the temperature reaches 800 ℃, the residual carbon content of the polyamide polymer containing triarylamine with propyl directly bonded with nitrogen atoms is 41-71%; further, it was found that the polymer had good thermal stability.
Claims (9)
1. The polyamide of triarylamine containing isopropyl directly bonded with nitrogen atom is characterized in that the polyamide of triarylamine containing isopropyl directly bonded with nitrogen atom is polyamide P1 containing triarylamine containing isopropyl directly bonded with nitrogen atom, polyamide P2 containing triarylamine containing isopropyl directly bonded with nitrogen atom, polyamide P3 containing triarylamine containing isopropyl directly bonded with nitrogen atom, polyamide P4 containing triarylamine containing isopropyl directly bonded with nitrogen atom or polyamide P5 containing triarylamine containing isopropyl directly bonded with nitrogen atom;
the structural formula of the triarylamine polyamide P1 containing isopropyl groups directly bonded to nitrogen atoms is as follows:
the polyamide P2 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P3 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P4 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
the polyamide P5 containing a triarylamine having isopropyl groups bonded directly to the nitrogen atom has the following structural formula:
wherein n is an integer of 12 to 21.
2. Process for the preparation of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 1: the method is characterized in that: the preparation method comprises the following steps:
one, synthesis of N1，N4-bis (4-aminophenyl) -N1-isopropyl-N4-phenyl benzene-1, 4-diamine monomer:
at N2Under the atmosphere, putting N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-neck flask, and stirring at 20 DEG CStirring for ten minutes, then adding p-fluoronitrobenzene at the dropping speed of 1-2 drops per second, heating to 115 ℃ for condensation reflux, and cooling after the constant-temperature reaction is finished; placing the reaction product in cold water until a crude product is separated out, filtering out the crude product, washing the crude product for 2-3 times, then recrystallizing by using ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain brick red powder M1;
wherein the molar volume ratio of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer to the anhydrous N, N-dimethylformamide is 10 mmol: (100-150) mL;
the mass ratio of sodium hydride to N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the molar ratio of the p-fluoronitrobenzene to the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer is 2: 1;
the molar volume ratio of the N-isopropyl-N-phenyl-1, 4-phenylenediamine monomer to cold water is 10 mmol: (400-450) mL;
the temperature of the vacuum drying is 80 ℃, the time of the vacuum drying is 36-48 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
② adding absolute ethyl alcohol, Pd/C and brick red powder M1 into a three-neck flask at room temperature, and introducing N into the three-neck flask2Dropwise adding hydrazine hydrate into the mixed solution in the three-necked bottle at a dropping speed of 1-2 drops per second by using a constant-pressure funnel; heating until the solution is refluxed, stopping heating after the reflux reaction is finished, filtering at 79-80 ℃ to remove Pd/C, pouring the filtrate into cold water, stirring while adding sodium chloride until solid is separated out, filtering the solid, washing with ethanol, and drying the filtered solid in vacuum to obtain triarylamine with isopropyl directly bonded with nitrogen atoms;
wherein the molar volume ratio of the brick red powder M1 to absolute ethyl alcohol is 10 mmol: (100-120) mL;
the mass ratio of the Pd/C to the amount of brick red powder M1 is (1-1.2) g: 5mmol of the active carbon;
the heating speed is 9-10 ℃ per minute when the temperature is raised until the solution flows back;
the ratio of the volume of hydrazine hydrate to the amount of material of brick red powder M1 was 3 mL: 1mmol of the active component;
the volume ratio of the filtrate to the cold water is 1: (3-4);
the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%;
the temperature of the vacuum drying is 28 ℃, the time of the vacuum drying is 48-60 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
secondly, preparing the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms:
triarylamine monomer with isopropyl directly bonded with nitrogen atom, diacid monomer, triphenyl phosphite, CaCl2Mixing pyridine and N-methylpyrrolidone, stirring for 3 hours at 119-120 ℃, cooling to room temperature, pouring into methanol, filtering to collect precipitate, fully washing with hot water and methanol, and performing Soxhlet extraction with methanol to obtain the product;
wherein the mass ratio of the triarylamine monomer and the diacid monomer, in which the isopropyl group is directly bonded to the nitrogen atom, is 1: 1;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the triphenyl phosphite is 1 mmol: 1.2 mL;
the molar volume ratio of the isopropyl group to the nitrogen atom directly bonded triarylamine monomer to pyridine is 1 mmol: 0.6 mL;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the N-methyl pyrrolidone is 1 mmol: 1.5 mL;
the CaCl is2The ratio of the mass of (b) to the volume of N-methylpyrrolidone is 0.15 g: 1.5 mL;
the molar volume ratio of the triarylamine monomer directly bonded with the isopropyl and the nitrogen atom to the methanol is 1 mmol: (200-250) mL.
3. Process for the preparation of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 2: the method is characterized in that: judging whether the constant-temperature reaction is finished or not by using a thin-layer chromatography, wherein a solvent used by the thin-layer chromatography is a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: (8-9).
4. Process for the preparation of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 2: the method is characterized in that: and in the second step, the diacid monomer is 4- (4-carboxyphenoxy) benzoic acid, terephthalic acid, 4' -dicarboxydiphenylsulfone, 1, 4-naphthalenedicarboxylic acid or 1, 4-cyclohexanedicarboxylic acid, and the polymers are respectively prepared into P1, P2, P3, P4 and P5.
5. Process for the preparation of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 2: the method is characterized in that: in step two, 300mL of methanol was used for 72 hours.
6. Process for the preparation of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 2: the method is characterized in that: the temperature of the cold water is 0 ℃, and the temperature of the hot water is 99-100 ℃.
7. Use of a polyamide containing a triarylamine having isopropyl groups directly bonded to nitrogen atoms as claimed in claim 1 as an electrochromic layer in an electrochromic device for electrochromic applications.
8. Use of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 7, wherein: the application of the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms as an electrochromic layer in an electrochromic device in electrochromism is carried out according to the following steps:
the method is characterized in that the polyamide containing triarylamine with isopropyl directly bonded with nitrogen atoms is used 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 generates electrochromism under the action of an external electric field.
9. Use of a polyamide containing a triarylamine having isopropyl groups directly bonded to the nitrogen atom, as claimed in claim 8, wherein: the conductive substrate is conductive glass, and the voltage of an external electric field is 0-1.60V.
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