CN116813899A - Flexible electrochromic composite material film and preparation method thereof - Google Patents
Flexible electrochromic composite material film and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 poly (aromatic amine ketone Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- DGMFCDNCHLSXNJ-UHFFFAOYSA-N 2-tert-butyl-N,N-diphenylaniline Chemical compound C(C)(C)(C)C1=C(C=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 DGMFCDNCHLSXNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 3
- 230000001681 protective effect Effects 0.000 claims 3
- 125000003277 amino group Chemical group 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 238000011161 development Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 17
- 239000007787 solid Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 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 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
A flexible electrochromic composite material film preparation method is characterized in that from the aspect of molecular design, a flexible polyaryletherketone-polyaryletherketone copolymer containing electrochromic polyaryletherketone structure is designed and synthesized, and the copolymer has good thermal stability, solubility and good mechanical property. Due to the similar main chain structure, the copolymer has good compatibility with the poly (aromatic amine ketone), can effectively reduce the glass transition temperature of the composite material, and can reduce the processing temperature of the material while endowing the film with good mechanical strength, thereby improving the electrochemical stability of the material. The composite material is easy to process into film and has excellent mechanical performance, so that the composite material has wide application range and practical value. According to the structural characteristics and photoelectric characteristics of the composite material film provided by the invention, the material can be expected to have wide development prospect and huge application potential in the photoelectric field, in particular in the aspects of electrochromic, information storage and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a flexible electrochromic composite material film and a preparation method thereof.
Background
Information system transmission display technology is widely used to mark people opening the "information age" of the beginning of the 21 st century, from which the lifestyle of humans has revolutionized and has become increasingly popular. The rapid development of information industry technology requires continuous improvement of technology process and development innovation of theoretical knowledge, and the development of novel materials can provide basis for theoretical research, can better meet the requirements of production process and promote the improvement of the production process, so that the development of novel functional materials becomes the key of the development of the field, wherein the development of novel organic polymer photoelectric functional materials has become important.
The polymer organic photoelectric functional material commonly used at present is mainly a conjugated polymer material, and the practical application of the polymer organic photoelectric functional material is limited due to high synthesis cost, poor solubility, deep neutral state color and the like. There is therefore an interest in backbone nonconjugated redox-type photopolymers, such as polyamides, polyimides, and the like. The polyaromatic ketone is used as a special engineering plastic, has excellent chemical stability and thermal stability, and is very suitable for becoming a main chain structure of a non-conjugated photoelectric material. Meanwhile, triphenylamine is a common compound with excellent photoelectric function, and the polymer photoelectric functional material constructed by the compound is widely applied to the photoelectric fields of hole transmission, electrochromic, electroluminescence, information storage, solar cells and the like because of good photoelectric activity, but the conventional polyarylketone polymer photoelectric functional material constructed by the triphenylamine compound is difficult to simultaneously achieve good photoelectric activity, electrochemical stability, thermal stability and processing solubility.
Disclosure of Invention
Based on the above, the invention provides a flexible electrochromic composite film and a preparation method thereof, so as to improve the photoelectric activity, electrochemical stability, thermal stability, solubility and mechanical properties of the polyarylketone polymer photoelectric functional material constructed by the triphenylamine compound at present.
In order to achieve the above object, the present invention provides a method for preparing a flexible electrochromic composite film, comprising the steps of:
a. synthesizing a flexible poly (aryl amine ketone) -poly (aryl ether ketone) copolymer in the composite material:
adding 4-amino-4 ', 4' -bis (tert-butyltriphenylamine), 6F bisphenol A, 4' -difluorobenzophenone, catalyst potassium carbonate, solvent and toluene with water into a reaction vessel, stirring and heating in nitrogen atmosphere for reaction, after the reaction reaches a certain time, rapidly rising the viscosity of the system, pouring reactants into deionized water for stopping the reaction, and finally crushing, washing and drying the solid obtained by the reaction to obtain the poly (aryl amine ketone) -poly (aryl ether ketone) copolymer, wherein the reaction formula is as follows:
wherein n is a polymerization degree, and an integer of 30 to 50 is taken; m is the copolymerization proportion, 0<m is less than or equal to 0.6.
The reaction charge amount of the catalyst potassium carbonate is preferably 2 times of the molar amount of 4,4' -difluorobenzophenone.
The solvent is sulfolane or N-methyl pyrrolidone.
b. Electrochromic polyaramidone in the composite was synthesized:
adding amino-containing monomer, 4' -difluorobenzophenone, catalyst potassium carbonate, solvent N-methylpyrrolidone and water-carrying agent toluene into a reaction vessel, stirring and heating in a nitrogen atmosphere for reaction, after the reaction reaches a certain time, rapidly rising the viscosity of the system, pouring reactants into deionized water for terminating the reaction, and finally crushing, washing and drying the solid obtained by the reaction to obtain electrochromic polyaramidone, wherein the reaction formula is as follows:
wherein n is a polymerization degree, and an integer of 30 to 50 is taken; ar is one of the following formulas (a) to (b):
in the formula (a) and the formula (b), R is methoxy or tert-butyl.
The reaction feeding amount of the catalyst potassium carbonate is preferably 2-3 times of the molar amount of 4,4' -difluorobenzophenone.
The solvent is sulfolane or N-methyl pyrrolidone.
The main chain of the electrochromic polyaramidone is polyaramidone, and according to different Ar structure selection, the electrochromic polyaramidone can be specifically in four structures shown in the following P1-P4:
c. c, mixing the flexible poly (aryl amine ketone) -poly (aryl ether ketone) copolymer obtained in the step a and the step b with electrochromic poly (aryl amine ketone) according to the mass ratio of 1:5-1:10 is dissolved in N-methyl pyrrolidone (NMP) or sulfolane to obtain a mixed solution with the concentration of 20mg/ml-100mg/ml, the mixed solution is spin-coated on ITO glass at the speed of 2000r/min, and the ITO glass is dried for 12 hours at the temperature of 120 ℃ in a vacuum oven to obtain the flexible electrochromic composite material film with good electrochromic performance.
Preferably, the reaction vessel in the step a and the step b is a three-neck flask with a nitrogen through hole, an oil-water separator and mechanical stirring, the reaction carried out in the reaction vessel is preferably carried out under the condition of dehydrating toluene with a water carrying agent, the temperature of the water carrying agent is 140-150 ℃, toluene is refluxed for 2-3h, toluene and water are discharged from the oil-water separator after the water carrying agent, the temperature of the reaction is increased to 200-220 ℃, and the reaction time is 30-40 h.
According to the flexible electrochromic composite material film and the preparation method thereof, from the aspect of molecular design, the flexible polyarylamine ketone-polyarylether ketone copolymer containing electrochromic polyarylamine ketone structures is designed and synthesized, and the copolymer has good thermal stability, solubility and good mechanical properties. Due to the similar main chain structure, the copolymer has good compatibility with the poly (aromatic amine ketone), can effectively reduce the glass transition temperature of the composite material, and can reduce the processing temperature of the material while endowing the film with good mechanical strength, thereby improving the electrochemical stability of the material. The composite material is easy to process into film and has excellent mechanical performance, so that the composite material has wide application range and practical value. According to the structural characteristics and photoelectric characteristics of the composite material film provided by the invention, the material can be expected to have wide development prospect and huge application potential in the photoelectric field, in particular in the aspects of electrochromic, information storage and the like.
Compared with common polyaramine materials, the flexible electrochromic composite material provided by the invention has the advantages that the novel copolymer is introduced, and the mechanical strength and the solubility of the material are effectively improved by the flexible chain segment. Meanwhile, the existence of the copolymer reduces pi-pi interaction among polyaramidone molecular chains, effectively reduces the processing temperature of the material, increases the free movement space of molecular chain segments, is beneficial to doping electrolyte anions and improves the electrochemical stability of the material. In a word, the flexible electrochromic composite material film has good mechanical property and good electrochemical stability, so that the flexible electrochromic composite material film has wide development prospect and great application potential in the photoelectric field.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a nuclear magnetic resonance spectrum of a poly (aryl amine ketone) -poly (aryl ether ketone) copolymer of 20% poly (aryl amine ketone) provided in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the polyarylene amine ketone P1 provided in example 2 of the present invention;
FIG. 3 is a differential scanning calorimetric spectrum of a composite film provided in example 4 of the present invention;
FIG. 4 is a graph of thermal weight loss under nitrogen protection of the composite film provided in example 4 of the present invention;
FIG. 5 is a graph of the cyclic voltammogram of a composite film provided in example 4 of the present invention;
FIG. 6 is an electrochromic UV absorption spectrum of the composite film provided in example 4 of the present invention at different voltages.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
Example 1:
the embodiment provides a synthesis method of a polyaramidone-polyaryletherketone copolymer containing 20% of polyaramidone, which comprises the following steps:
4-amino-4 ', 4' -bis-t-butyltriphenylamine (3.323 g,10 mmol), 4' -difluorobenzophenone (10.910 g,50 mmol), 6F bisphenol A (13.442 g,40 mmol) as catalyst potassium carbonate (13.823 g,100 mmol), 73mL sulfolane (solid content 25%), 20mL toluene as a water-carrying agent were put into a 250mL three-necked flask equipped with a nitrogen port, an oil-water separator and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene was refluxed for 3 hours, and after sufficient water carrying, toluene and water were discharged by using the oil-water separator. Then the temperature is increased to 220 ℃ and the stirring reaction is carried out for 3 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with a tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times each 800 mL) and ethanol (3 times each 300 mL), washing, filtering, collecting, standing in oven, and drying at 80deg.C for 10 hr. Pale yellow polymer powder (21.757 g, 90% yield) was obtained.
The polymer obtained in this example was subjected to structural analysis, and the nuclear magnetic hydrogen spectrum of the obtained product was shown in FIG. 1. The nuclear magnetic hydrogen spectrum chemical shift distribution of the poly (aryl amine ketone) -poly (aryl ether ketone) copolymer of 20% poly (aryl amine ketone) can be seen in FIG. 1, and particularly the peak of the tertiary butyl at 1.31ppm is clearly seen, which proves the successful preparation of the polymer.
Example 2:
the embodiment provides a synthesis method of electrochromic polyaramidone P1:
4-amino-4 ', 4' -Dimethoxytriphenylamine (3.20 g,10 mmol), 4' -difluorobenzophenone (2.180 g,10 mmol), potassium carbonate (2.76 g,20 mmol), 21mL of N-methylpyrrolidone (solid content: 20%), and 10mL of toluene as a water-carrying agent were put into a 100mL three-necked flask equipped with a nitrogen port, an oil-water separator, and mechanical stirring, heated to reflux of toluene in a nitrogen atmosphere for 3 hours, and toluene and water were discharged by using the oil-water separator after sufficient water carrying. Then the temperature is increased to 200 ℃ and the reaction is stirred for 35 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with a tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times each 800 mL) and ethanol (3 times each 300 mL), washing, filtering, collecting, standing in oven, and drying at 80deg.C for 10 hr. A pale yellow polymer powder (4.312 g, 80% yield) was obtained.
The polymer obtained in this example was subjected to structural analysis, and the nuclear magnetic hydrogen spectrum of the obtained product was shown in FIG. 2. In FIG. 2, it can be seen that the nuclear magnetic hydrogen spectral chemical shift of the polymer P1 is likewise clearly distributed, wherein the nuclear magnetic hydrogen spectral peak at 4.02ppm is methoxy, demonstrating the successful preparation of the polymer.
Example 3:
the embodiment provides a synthesis method of electrochromic polyaramidone P4:
3, 6-bis-t-butyl-9- (4-amino) carbazole (3.70 g,10 mmol), 4' -difluorobenzophenone (2.180 g,10 mmol), potassium carbonate (2.76 g,20 mmol), 22mL of N-methylpyrrolidone (solid content: 20%), 10mL of toluene with water agent were put into a 100mL three-necked flask equipped with a nitrogen port, an oil-water separator and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene was refluxed for 3 hours, and after sufficient water was taken, toluene and water were discharged by using the oil-water separator. Then the temperature is increased to 200 ℃ and the reaction is stirred for 35 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with a tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times each 800 mL) and ethanol (3 times each 300 mL), washing, filtering, collecting, standing in oven, and drying at 80deg.C for 10 hr. Pale yellow polymer powder (4.433 g, 82% yield) was obtained.
The nuclear magnetic hydrogen spectrum data of the product obtained in this example are: 1H NMR (300 MHz, CDCl 3): d nearest 8.13(s), 7.88-7.85 (d), 7.55 (br), 7.49-7.37 (br), 7.33-7.25 (br), 1.44(s).
Example 4:
the embodiment provides a preparation method of a flexible electrochromic composite material film.
1. 20mg of the 20% poly (arylene amine ketone) -poly (arylene ether ketone) copolymer prepared in example 1 and 100mg of the polymer P1 prepared in example 2 were added to 5ml of NMP, and heated at 60℃until they were sufficiently dissolved to obtain a mixed solution.
2. The mixed solution is filtered twice by using a nylon needle filter with the diameter of 0.22 mu m, and then the mixed solution is spin-coated on ITO glass at the speed of 2000r/min, and is dried for 12 hours at the temperature of 120 ℃ in a vacuum oven, so that the flexible electrochromic composite material film (short for composite film) with good electrochromic performance is obtained.
The thermal stability of the obtained composite film is shown in fig. 3 and 4, the electrochemical properties are shown in fig. 5, and the electrochromic capability performance is shown in fig. 6.
In fig. 3, it can be seen that the glass transition temperature of the composite film has only one peak at 224 degrees celsius, which indicates that the thermal stability of the material is good, and the compatibility of the two materials is good.
The thermal decomposition temperature of the composite film can be seen in fig. 4 at 590 degrees celsius, again demonstrating good thermal stability of the material.
In fig. 5, it can be seen that the composite film still maintains good peak shape and peak position after 1000 cyclic voltammetry tests, and the electrochemical stability of the material is proved to be good.
The change in the ultraviolet absorbance spectrum of the composite film at different potentials can be seen in fig. 6, demonstrating that the material has good electrochromic capability.
Example 5:
the embodiment provides a preparation method of a flexible electrochromic composite material film.
1. 20mg of the 20% poly (arylene amine ketone) -poly (arylene ether ketone) copolymer prepared in example 1 and 200mg of the polymer P4 prepared in example 3 were added to 5ml of NMP, and heated at 60℃until they were sufficiently dissolved to obtain a mixed solution.
2. Filtering the mixed solution twice by using a nylon needle filter with the diameter of 0.22 mu m, spin-coating the mixed solution on ITO glass at the speed of 2000r/min, and drying the mixed solution in a vacuum oven at the temperature of 120 ℃ for 12 hours to obtain the flexible electrochromic composite material film with good electrochromic performance.
Solubility test
The solubility of a series of polymers prepared according to the invention was tested, the solvents used and the results of the tests are shown in table 1:
table 1 solubility test table
The solubility test demonstrates that the polymer P1 has significantly improved solubility after incorporation into 20% of the copolymer, especially in lower boiling solvents. The material can be used for removing the solvent at a lower temperature, so that the energy consumption is reduced, and the cost is reduced. Meanwhile, better solubility means less precipitation in the spin coating process of the material, which is favorable for forming a smoother surface morphology of the film, namely, the performance of the material is improved.
The experimental results show that: the flexible electrochromic composite material film provided by the invention has a 5% thermal weight loss of more than 550 ℃, can be dissolved in organic solvents such as tetrahydrofuran, dichloromethane, chloroform, N '-Dimethylformamide (DMF), N' -dimethylformamide (DMAc), N-methylpyrrolidone (NMP) and the like, and can show the photoelectric characteristics of corresponding photoelectric active groups.
The products obtained in example 4 and example 5 were compared and the thermal stability, electrochemical properties, electrochromic capacity and solubility of both were close. In addition, electrochromic polyaramidone P1 and P2, and P3 and P4 are only R groups selected differently, which are respectively applied to the preparation of the flexible electrochromic composite film of the invention, and the obtained composite film has various properties close to each other. Therefore, the invention realizes the purpose of improving the photoelectric activity, electrochemical stability, thermal stability, solubility and mechanical property of the polyarylketone high molecular photoelectric functional material constructed by the prior triphenylamine compound, and simultaneously combines good photoelectric activity, electrochemical stability, thermal stability and processing solubility.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (9)
1. The preparation method of the flexible electrochromic composite material film is characterized by comprising the following steps of:
s1, mixing 4-amino-4 ', 4' -bis (tert-butyltriphenylamine), 6F bisphenol A, 4' -difluorobenzophenone, catalyst potassium carbonate, solvent and toluene with water, and stirring for reaction in a protective gas atmosphere to obtain a flexible polyaramidone-polyaryletherketone copolymer;
s2, mixing an amino group-containing monomer, 4' -difluorobenzophenone, catalyst potassium carbonate, a solvent and toluene with a water-carrying agent, and stirring and reacting in a protective gas atmosphere to obtain electrochromic polyaramidone, wherein the structural formula of the amino group-containing monomer is as follows:
wherein Ar is one of the following formulas (a) or (b):
in the formula (a) and the formula (b), R is methoxy or tert-butyl;
s3, dissolving the flexible poly (aryl amine ketone) -poly (aryl ether ketone) copolymer and electrochromic poly (aryl amine ketone) in a solvent to form a mixed solution, coating the mixed solution on ITO glass, and vacuum drying to obtain the flexible electrochromic composite material film with good electrochromic performance.
2. The method for preparing a flexible electrochromic composite film according to claim 1, wherein the flexible polyaryletherketone-ketone copolymer obtained in the step S1 comprises the following structural segment of formula (I):
in the formula (I), n is the polymerization degree, and an integer of 30-50 is taken; m is the copolymerization proportion, 0<m is less than or equal to 0.6.
3. The method for preparing a flexible electrochromic composite film according to claim 1, wherein the electrochromic polyaramidone obtained in step S2 comprises a structural segment of formula (ii):
in the formula (II), n is the polymerization degree, and an integer of 30-50 is taken; ar is one of the following formulas (a) or (b):
in the formula (a) and the formula (b), R is methoxy or tert-butyl.
4. The method for preparing a flexible electrochromic composite film according to claim 1, wherein the stirring reaction process in the protective gas atmosphere in steps S1 and S2 is equally performed in two steps: stirring and heating to 140-150 ℃ to reflux toluene for 2-3h, discharging toluene and water by adopting an oil-water separator after fully carrying water, and then stirring and reacting for 3-8h after raising the temperature to 200-220 ℃.
5. The method for preparing a flexible electrochromic composite film according to claim 4, wherein the reaction vessel used for stirring reaction in the steps S1 and S2 is a three-necked flask equipped with a nitrogen port, an oil-water separator and mechanical stirring.
6. The method for preparing a flexible electrochromic composite film according to claim 1, wherein the reaction dosage of the catalyst potassium carbonate in the steps S1 and S2 is 2-3 times of the molar amount of 4,4' -difluorobenzophenone in the corresponding step.
7. The method for preparing a flexible electrochromic composite film according to claim 1, wherein in the step S3, the flexible polyaryletherketone-polyaryletherketone copolymer and the electrochromic polyaryletherketone are mixed according to a mass ratio of 1:5-1:10 and dissolved in a solvent, and the concentration of the obtained mixed solution is 20-100mg/ml.
8. The method for preparing a flexible electrochromic composite film according to claim 1, wherein the solvent used in steps S1, S2 and S3 is N-methylpyrrolidone or sulfolane.
9. A flexible electrochromic composite film prepared by the method of any one of claims 1-8.
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