CN111362867B - Mobile terminal, shell assembly, electrochromic material and preparation method thereof - Google Patents
Mobile terminal, shell assembly, electrochromic material and preparation method thereof Download PDFInfo
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- 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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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
- H04M1/0279—Improving the user comfort or ergonomics
- H04M1/0283—Improving the user comfort or ergonomics for providing a decorative aspect, e.g. customization of casings, exchangeable faceplate
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/72—Mobile telephones; Cordless telephones, i.e. devices for establishing wireless links to base stations without route selection
- H04M1/724—User interfaces specially adapted for cordless or mobile telephones
- H04M1/72448—User interfaces specially adapted for cordless or mobile telephones with means for adapting the functionality of the device according to specific conditions
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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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
Abstract
The invention relates to an electrochromic material, which is an ion pair compound consisting of a functional group with a cathode electrochromic function and a functional group with an anode electrochromic function, wherein the ion pair compound has a chemical structural general formula shown in a formula (I); the functional groups with the cathode electrochromic function are a perfluoroalkyl group and a bipyridyl salt modified by a hydroxyl group, and the functional groups with the anode electrochromic function are a benzotriazole derivative and a phenazine derivative modified by a bisphenylsulfonic acid group. The electrochromic material has the advantages of aging resistance, high response speed and high contrast. The invention also discloses a shell component comprising the electrochromic material and a mobile terminal, which meet the requirement of the mobile terminal on appearance integrity and have great market application prospect.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to a mobile terminal, a shell component, an electrochromism material and a preparation method thereof.
Background
With the continuous development of network communication technology, smart phones are more and more widely used. Mobile terminals such as smart phones, IPADs and the like are generally provided with optical devices (camera modules, ambient light sensors, flash lamps and the like), and the optical devices need to be provided with light-transmitting areas at corresponding positions on the mobile terminals so as to receive and reflect light. The light-transmitting area on the existing mobile terminal is transparent, the color changing effect of the light-transmitting area on incident light cannot be realized through the control of the mobile terminal, the appearance integrity of the mobile terminal is easily damaged by the light-transmitting area, and the visual attractiveness of the mobile terminal is reduced.
Disclosure of Invention
In view of the defects of the prior art, the invention provides an electrochromic material and a preparation method thereof; the electrochromic material is an ion pair compound consisting of a functional group with a cathode electrochromic function and a functional group with an anode electrochromic function, and the ion pair compound has a chemical structural general formula shown in a formula (I):
in the formula:
r1 is a perfluoroalkyl chain with 4-12 carbon atoms;
r2 is alkanyl with 2 to 16 carbon atoms;
r3 is a chain alkyl group of 1 to 2 carbon atoms;
r4 and R5 are the same or different groups, and can be selected from one of H, cl, F, phenyl, methoxy, ethoxy and propoxy.
On one hand, the cathode electrochromic material provided by the application is characterized in that a chain segment is grafted through nucleophilic substitution of two nitrogen atoms on 4,4' -bipyridine, the terminal groups of the chain segment are a perfluoro functional group and a hydroxyl group respectively, and the hydrophobic property of the perfluoro functional group and the hydrophilic property of the hydroxyl group are utilized, so that the cathode electrochromic material can be in an ordered arrangement state in an electrochromic solution, and the response speed of the electrochromic material is promoted; on the other hand, the anode electrochromic material is characterized in that two nitrogen atoms on phenazine are symmetrically grafted with chain segments with benzenesulfonic acid functional groups, so that sulfonate anions of the anode electrochromic material and cations of the cathode electrochromic material are paired to form an ion pair compound, ion transmission and electron conduction of the electrochromic material are facilitated, and the response speed of the electrochromic material is further improved. The phenazine main structure with the anode electrochromic function is grafted with a benzotriazole derivative, has a strong absorption effect on ultraviolet light with the wavelength of 300-400 nm, hardly absorbs visible light with the wavelength of more than 400nm, and further cannot cause yellowing of an electrochromic material, so that the aging resistance of the electrochromic material is improved, and the service life of a shell component is prolonged. The electrochromic material of the ion pair compound also has the advantage of high contrast.
A method for preparing the electrochromic material, which comprises the following steps:
s1: mixing 4,4' -bipyridine with a solvent according to a mass ratio of 1: 3-20, then adding a compound with a structural formula (b) for chemical reaction, controlling the reaction temperature to be 40-80 ℃ and the reaction time to be 2-144 h to obtain a mixed solution A containing a bipyridine salt intermediate product with a structural formula (c);
s2: adding a compound with a structural formula (d) into the mixed solution A obtained in the step S1 to perform a chemical reaction, performing heating condensation reflux reaction at the temperature of 40-80 ℃, reacting for 2-48 h, and performing crystallization separation to obtain a bipyridine salt compound with a structural formula (II);
s3: dissolving nitroaniline with the structural formula (e) in a hydrochloric acid solution, cooling to 0-10 ℃, then slowly adding a sodium nitrite solution, and carrying out diazotization reaction to obtain a reaction product with the structural formula (f), wherein the molar ratio of the nitroaniline with the structural formula (e) to the hydrochloric acid to the sodium nitrite is 1: 2-2.5: 1 to 1.2; and meanwhile, dissolving catechol into a sodium hydroxide solution to obtain catechol sodium salt, wherein the molar ratio of the catechol to the sodium hydroxide is 1:2 to 2.2; and adding the reaction product with the structural formula (f) and sodium pyrocatechol salt into a sodium carbonate solution for coupling reaction, stopping the reaction when the alkalinity of the reaction materials is not reduced, and filtering to obtain a reaction product with the structural formula (g), wherein the molar ratio of the reaction product with the structural formula (f) to the sodium pyrocatechol salt and the sodium carbonate is 2: 2-2.2: 1 to 1.2; adding the reaction product with the structural formula (g) into a proper amount of sodium hydroxide alkali liquor, uniformly stirring, adding zinc powder, carrying out reduction reaction, filtering to remove residues such as the zinc powder after the reaction is completed, adding hydrochloric acid at normal temperature for acidification, crystallizing, and filtering to obtain a compound with the structural formula (h); and finally, reacting the compound with the structural formula (h) with o-phenylenediamine in a heating tube to obtain the phenazine derivative with the structural formula (i), wherein the molar ratio of the compound with the structural formula (h) to the o-phenylenediamine is 1:1 to 1.1;
s4: mixing a phenazine derivative with a structural formula (i) and a solution consisting of sodium hydrosulfite, sodium carbonate and a small amount of water according to a mass ratio of 1: 4-40, stirring and mixing uniformly, then adding a compound with a structural formula (j) for chemical reaction, and carrying out heating condensation reflux reaction at the temperature of 40-80 ℃ for 2-48 h to obtain a mixed solution B containing a phenazine sodium salt compound with a structural formula (III); carrying out ion exchange on the mixed solution B and silver nitrate, and carrying out crystallization separation to obtain a phenazine silver salt compound with a structural formula (IV); the mass ratio of the sodium hydrosulfite to the sodium carbonate is 3:1, the addition of a small amount of water can ensure that sodium hydrosulfite and sodium carbonate are dissolved;
s5: the bipyridine salt compound of formula (II) obtained in step S2 and the phenazine silver salt compound of formula (IV) obtained in step S4 are mixed in a molar ratio of 1:1, adding the mixture into an ethanol solution, reacting to separate out silver halide precipitate, and after separating the precipitate, carrying out reduced pressure distillation on the upper layer liquid to obtain a target product with a structural formula (I);
in the formula:
r1 is a perfluoroalkyl chain with 4-12 carbon atoms;
r2 is a chain alkyl group of 2 to 16 carbon atoms;
r3 is a chain alkyl group of 1 to 2 carbon atoms;
r4 and R5 are the same or different groups, and can be selected from one of H, cl, F, methyl, ethyl, phenyl, methoxy, ethoxy and propoxy.
As a preferred technical solution, the molar ratio of the compound 4,4' -bipyridine of structural formula (a) to the compound of structural formula (b) is 1:1; the molar ratio of the compound with the structural formula (d) to the bipyridyl salt intermediate product with the structural formula (c) is 1:1.
in step S1, the solvent is one or more of tetrahydrofuran, acetonitrile, toluene, xylene, DMF, and ethyl acetate.
Further, the compound with the structural formula (b) is prepared by the following steps: 1-bromo-3-buten-2-ol and perfluoroalkyl ethylene are mixed according to a molar ratio of 1:1, adding dibenzoyl peroxide and an ethanol aqueous solution into a reaction kettle, heating to 60-120 ℃, carrying out heating condensation reflux reaction, and standing and separating after the reaction is finished to obtain the compound with the structural formula (b). The percentage of the added amount of dibenzoyl peroxide in the total mass of the 1-bromo-3-buten-2-ol and the perfluoroalkyl ethylene is 0.01-0.05%, and the mass ratio of the added amount of the ethanol aqueous solution to the 1-bromo-3-buten-2-ol is 3-10: 1.
preferably, the perfluoroalkyl ethylene is one of perfluorobutyl ethylene, 1H, 2H-perfluoro-1-decene, perfluorohexylethylene, perfluorodecylethylene and perfluorododecylethylene.
As a preferred technical scheme, the compound with the structural formula (d) is one of 2-iodoethanol, 3-iodopropanol, 1-bromo-2-propanol, 3-bromo-1-propanol, 1-bromo-2-butanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-n-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 11-bromo-1-undecanol, 12-bromo-1-dodecanol, 13-bromotridecane-1-ol, 14-bromotetradecan-1-ol, 16-bromohexadecan-1-ol, 2-chloroethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-nonanol, 9-chloro-1-nonanol and 10-chloro-1-decanol.
As a preferred technical scheme, the nitroaniline with the structural formula (e) is one of 5-chloro-4-fluoro-2-nitroaniline, 5-chloro-2-nitroaniline, 4-chloro-5-methyl-2-nitro-aniline, 4-chloro-2-nitroaniline, 5-ethoxy-4-fluoro-2-nitroaniline, 5-fluoro-2-nitroaniline, 4-fluoro-2-nitroaniline, 4,5-difluoro-2-nitroaniline, 4- (3-nitrophenyl) aniline, 5-methoxy-2-nitroaniline, 4-methoxy-5-methyl-2-nitroaniline, 4,5-dimethoxy-2-nitroaniline, 4-methoxy-2-nitroaniline, 4,5-diethoxy-2-nitroaniline, 4-ethoxy-5-fluoro-2-nitroaniline, 4-ethoxy-5-ethyl-2-nitroaniline, 4-ethoxy-2-nitroaniline and 2-nitro-4-propoxy-aniline.
In another aspect, the present invention provides a housing assembly including a housing and an electrochromic unit module disposed on the housing, the electrochromic unit module including:
a first substantially transparent conductive substrate;
a second substantially transparent conductive substrate, the first and second conductive substrates being disposed in a spaced apart relationship and defining a cavity; and
the electrochromic material is arranged in the cavity.
The invention also provides a mobile terminal which comprises a camera and the shell assembly, wherein the camera and the electrochromic unit module are arranged on the mobile terminal in a facing way; when the mobile terminal does not start the camera shooting function, the electrochromic unit module is in a coloring state; and when the mobile terminal starts a camera shooting function, the electrochromic unit module is in a fading state.
Compared with the prior art, the invention has the beneficial effects that:
the electrochromic material is an ion pair compound with a chemical structure general formula shown in a formula (I); the functional group with the cathode electrochromic function is a perfluoroalkyl group and a bipyridyl salt modified by a hydroxyl group, and the functional group with the anode electrochromic function is a phenazine derivative modified by a bisphenylsulfonic acid group, so that the method has the advantages of high response speed and high contrast.
According to the electrochromic material, the phenazine main body structure with the anode electrochromic function is further grafted with a benzotriazole derivative, so that the aging resistance of the electrochromic material is further improved, and the service life of a shell component is prolonged.
The utility model provides a shell subassembly and contain cell-phone of this shell subassembly is provided with electrochromic unit module, through the quick response and the high contrast of electrochromic unit module, can hide the inside camera of cell-phone when realizing that electrochromic unit module is painted and not perceived the function, and can satisfy the effect of the inside camera normal function of making a video recording of cell-phone when it fades, and then improve cell-phone outward appearance wholeness.
Drawings
Fig. 1 is a front view of a mobile terminal according to an embodiment of the present invention;
fig. 2 is a rear view of a mobile terminal according to an embodiment of the present invention;
fig. 3 isbase:Sub>A sectional view of the electrochromic cell module in fig. 2 taken alongbase:Sub>A-base:Sub>A direction.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments described below are by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the electrochromic material of the embodiment comprises the following steps:
s1: mixing 4,4' -bipyridine with tetrahydrofuran according to the mass ratio of 1:10, stirring and mixing uniformly, then adding a compound with a structural formula (b) to carry out a chemical reaction, controlling the reaction temperature to be 60 ℃ and the reaction time to be 72 hours, and obtaining a mixed solution A containing a bipyridyl salt intermediate product with a structural formula (c);
s2: adding 2-iodoethanol of a compound shown in a structural formula (d) into the mixed solution A obtained in the step S1 to perform chemical reaction, performing heating condensation reflux reaction at the temperature of 60 ℃, performing reaction for 24 hours, cooling, adding toluene to precipitate a reactant, filtering, and recrystallizing with hot ethanol (the hot ethanol in the invention refers to ethanol with the temperature of about 45-55 ℃) to obtain a bipyridine salt compound shown in a structural formula (II);
s3: dissolving nitroaniline with the structural formula (e) in a hydrochloric acid solution, cooling to 0-10 ℃, then slowly adding a sodium nitrite solution, and carrying out diazotization reaction to obtain a reaction product with the structural formula (f), wherein the molar ratio of the nitroaniline with the structural formula (e) to the hydrochloric acid to the sodium nitrite is 1:2:1; and simultaneously dissolving catechol in a sodium hydroxide solution to obtain catechol sodium salt, wherein the molar ratio of catechol to sodium hydroxide is 1:2.1; and adding the reaction product with the structural formula (f) and sodium pyrocatechol salt into a sodium carbonate solution for coupling reaction, stopping the reaction when the alkalinity of the reaction materials is not reduced, and filtering to obtain a reaction product with the structural formula (g), wherein the molar ratio of the reaction product with the structural formula (f) to the sodium pyrocatechol salt and the sodium carbonate is 2:2:1.1; adding the reaction product with the structural formula (g) into a proper amount of sodium hydroxide alkali liquor, uniformly stirring, adding zinc powder, carrying out reduction reaction, filtering to remove residues such as the zinc powder after the reaction is completed, adding hydrochloric acid at normal temperature for acidification, crystallizing, and filtering to obtain a compound with the structural formula (h); and finally, reacting the compound with the structural formula (h) with o-phenylenediamine in a heating tube to obtain the phenazine derivative with the structural formula (i), wherein the molar ratio of the compound with the structural formula (h) to the o-phenylenediamine is 1:1;
s4: mixing a phenazine derivative represented by the formula (i) with a solution composed of sodium dithionite, sodium carbonate and a small amount of water (the solution composed of sodium dithionite, sodium carbonate and a small amount of water in the present invention means a solution containing 30wt% of diethyl ether composed of sodium dithionite, sodium carbonate and a small amount of water) in a mass ratio of 1:20, stirring and mixing uniformly, then adding a compound with a structural formula (j) for chemical reaction, and carrying out heating condensation reflux reaction at the temperature of 60 ℃ for 24 hours to obtain a mixed solution B containing a phenazine sodium salt compound with a structural formula (III); carrying out ion exchange on the mixed solution B and silver nitrate, and carrying out crystallization separation to obtain a phenazine silver salt compound with a structural formula (IV); the mass ratio of the sodium hydrosulfite to the sodium carbonate is 3:1, the addition of a small amount of water can ensure that sodium hydrosulfite and sodium carbonate are dissolved;
s5: the bipyridine salt compound of formula (II) obtained in step S2 and the phenazine silver salt compound of formula (IV) obtained in step S4 are mixed in a molar ratio of 1:1, adding the mixture into an ethanol solution, reacting to separate out silver halide precipitate, and carrying out reduced pressure distillation on the upper layer liquid after the precipitate is separated to obtain a target product with a structural formula (I);
in the formula:
r1 is a perfluoroalkyl chain of 4 carbon atoms;
r2 is an alkanyl radical of 2 carbon atoms;
r3 is an alkanyl radical of 1 carbon atom;
r4 is Cl and R5 is F.
The molar ratio of the compound 4,4' -bipyridine of structural formula (a) to the compound of structural formula (b) is 1:1; the molar ratio of the compound with the structural formula (d) to the bipyridyl salt intermediate product with the structural formula (c) is 1:1.
the preparation method of the compound with the structural formula (b) comprises the following steps: 1-bromo-3-buten-2-ol and perfluorobutyl ethylene are mixed according to a molar ratio of 1:1, adding dibenzoyl peroxide and an ethanol aqueous solution into a reaction kettle, heating to 90 ℃, carrying out heating condensation reflux reaction, and standing for separation after the reaction is finished to obtain the compound with the structural formula (b).
The nitroaniline with the structural formula (e) is 5-chloro-4-fluoro-2-nitroaniline.
Example 2
The preparation method of the electrochromic material of the embodiment comprises the following steps:
s1: mixing 4,4' -bipyridine with toluene according to the mass ratio of 1:3, uniformly stirring and mixing, then adding a compound with a structural formula (b) to carry out a chemical reaction, controlling the reaction temperature to be 60 ℃ and the reaction time to be 144 hours, and obtaining a mixed solution A containing a bipyridyl salt intermediate product with a structural formula (c);
s2: adding 16-bromohexadecan-1-ol of the compound shown in the structural formula (d) into the mixed solution A obtained in the step S1 to perform chemical reaction, performing heating condensation reflux reaction at the temperature of 60 ℃, cooling, adding toluene to precipitate a reactant, filtering, and recrystallizing with hot ethanol to obtain a bipyridine salt compound shown in the structural formula (II);
s3: dissolving nitroaniline with the structural formula (e) in a hydrochloric acid solution, cooling to 0-10 ℃, then slowly adding a sodium nitrite solution, and carrying out diazotization reaction to obtain a reaction product with the structural formula (f), wherein the molar ratio of the nitroaniline with the structural formula (e) to the hydrochloric acid to the sodium nitrite is 1:2.3:1.1; and simultaneously dissolving catechol in a sodium hydroxide solution to obtain catechol sodium salt, wherein the molar ratio of catechol to sodium hydroxide is 1:2.1; and adding the reaction product with the structural formula (f) and sodium pyrocatechol salt into a sodium carbonate solution for coupling reaction, stopping the reaction when the alkalinity of the reaction materials is not reduced, and filtering to obtain a reaction product with the structural formula (g), wherein the molar ratio of the reaction product with the structural formula (f) to the sodium pyrocatechol salt and the sodium carbonate is 2:2:1; adding the reaction product with the structural formula (g) into a proper amount of sodium hydroxide alkali liquor, uniformly stirring, adding zinc powder, carrying out reduction reaction, filtering to remove residues such as the zinc powder after the reaction is completed, adding hydrochloric acid at normal temperature for acidification, crystallizing, and filtering to obtain a compound with the structural formula (h); and finally, reacting the compound with the structural formula (h) with o-phenylenediamine in a heating tube to obtain the phenazine derivative with the structural formula (i), wherein the molar ratio of the compound with the structural formula (h) to the o-phenylenediamine is 1:1.05;
s4: mixing a phenazine derivative with a structural formula (i) and a solution consisting of sodium hydrosulfite, sodium carbonate and a small amount of water according to a mass ratio of 1:40, uniformly stirring and mixing, then adding a compound with a structural formula (j) for chemical reaction, and carrying out heating condensation reflux reaction at the temperature of 60 ℃ for 36 hours to obtain a mixed solution B containing a phenazine sodium salt compound with a structural formula (III); carrying out ion exchange on the mixed solution B and silver nitrate, and carrying out crystallization separation to obtain a phenazine silver salt compound with a structural formula (IV); the mass ratio of the sodium hydrosulfite to the sodium carbonate is 3:1, the addition of a small amount of water can ensure that sodium hydrosulfite and sodium carbonate are dissolved;
s5: the bipyridine salt compound of formula (II) obtained in step S2 and the phenazine silver salt compound of formula (IV) obtained in step S4 are mixed in a molar ratio of 1:1, adding the mixture into an ethanol solution, reacting to separate out silver halide precipitate, and after separating the precipitate, carrying out reduced pressure distillation on the upper layer liquid to obtain a target product with a structural formula (I);
in the formula:
r1 is a perfluoroalkyl chain of 12 carbon atoms;
r2 is alkanyl with 16 carbon atoms;
r3 is an alkanyl radical of 2 carbon atoms;
r4 is Cl and R5 is H.
The molar ratio of the compound 4,4' -bipyridine with the structural formula (a) to the compound with the structural formula (b) is 1:1; the molar ratio of the compound with the structural formula (d) to the bipyridine salt intermediate product with the structural formula (c) is 1:1; the molar ratio of the compound phenazine with the structural formula (e) to the compound with the structural formula (f) is 1:2.
the preparation method of the compound with the structural formula (b) comprises the following steps: 1-bromo-3-buten-2-ol and perfluorododecyl ethylene are mixed according to a molar ratio of 1:1, adding dibenzoyl peroxide and an ethanol aqueous solution into a reaction kettle, heating to 100 ℃, carrying out heating condensation reflux reaction, and standing for separation after the reaction is finished to obtain the compound with the structural formula (b).
The nitroaniline with the structural formula (e) is 5-chloro-2-nitroaniline.
Example 3
The preparation method of the electrochromic material of the embodiment comprises the following steps:
s1: mixing 4,4' -bipyridine with acetonitrile according to the mass ratio of 1:20, stirring and mixing uniformly, then adding a compound with a structural formula (b) to carry out a chemical reaction, controlling the reaction temperature to be 80 ℃ and the reaction time to be 144 hours, and obtaining a mixed solution A containing a bipyridyl salt intermediate product with a structural formula (c);
s2: adding a compound 8-bromo-1-octanol with a structural formula (d) into the mixed solution A in the step S1 to perform a chemical reaction, performing heating condensation reflux reaction at the temperature of 60 ℃, cooling, adding toluene to precipitate a reactant, filtering, and recrystallizing with hot ethanol to obtain a bipyridine salt compound with a structural formula (II);
s3: dissolving nitroaniline with the structural formula (e) in a hydrochloric acid solution, cooling to 0-10 ℃, then slowly adding a sodium nitrite solution, and carrying out diazotization reaction to obtain a reaction product with the structural formula (f), wherein the molar ratio of the nitroaniline with the structural formula (e) to the hydrochloric acid to the sodium nitrite is 1:2:1.1; and simultaneously dissolving catechol in a sodium hydroxide solution to obtain catechol sodium salt, wherein the molar ratio of catechol to sodium hydroxide is 1:2.1; and adding the reaction product with the structural formula (f) and sodium pyrocatechol salt into a sodium carbonate solution for coupling reaction, stopping the reaction when the alkalinity of the reaction materials is not reduced, and filtering to obtain a reaction product with the structural formula (g), wherein the molar ratio of the reaction product with the structural formula (f) to the sodium pyrocatechol salt and the sodium carbonate is 2:2:1.1; adding the reaction product with the structural formula (g) into a proper amount of sodium hydroxide alkali liquor, uniformly stirring, adding zinc powder, carrying out reduction reaction, filtering to remove residues such as the zinc powder after the reaction is completed, adding hydrochloric acid at normal temperature for acidification, crystallizing, and filtering to obtain a compound with the structural formula (h); and finally, reacting the compound with the structural formula (h) with o-phenylenediamine in a heating tube to obtain the phenazine derivative with the structural formula (i), wherein the molar ratio of the compound with the structural formula (h) to the o-phenylenediamine is 1:1.1;
s4: mixing a phenazine derivative with a structural formula (i) and a solution consisting of sodium hydrosulfite, sodium carbonate and a small amount of water according to a mass ratio of 1:4, stirring and mixing uniformly, then adding a compound with a structural formula (j) for chemical reaction, and carrying out heating condensation reflux reaction at the temperature of 60 ℃ for 48 hours to obtain a mixed solution B containing a phenazine sodium salt compound with a structural formula (III); carrying out ion exchange on the mixed solution B and silver nitrate, and carrying out crystallization separation to obtain a phenazine silver salt compound with a structural formula (IV); the mass ratio of the sodium hydrosulfite to the sodium carbonate is 3:1, the addition of a small amount of water can ensure that sodium hydrosulfite and sodium carbonate are dissolved;
s5: the bipyridine salt compound of formula (II) obtained in step S2 and the phenazine silver salt compound of formula (IV) obtained in step S4 are mixed in a molar ratio of 1:1, adding the mixture into an ethanol solution, reacting to separate out silver halide precipitate, and after separating the precipitate, carrying out reduced pressure distillation on the upper layer liquid to obtain a target product with a structural formula (I);
in the formula:
r1 is a perfluoroalkyl chain of 6 carbon atoms;
r2 is an alkanyl radical of 8 carbon atoms;
r3 is an alkanyl radical of 2 carbon atoms;
r4 is methyl and R5 is Cl.
The molar ratio of the compound 4,4' -bipyridine of structural formula (a) to the compound of structural formula (b) is 1:1; the molar ratio of the compound with the structural formula (d) to the bipyridyl salt intermediate product with the structural formula (c) is 1:1; the molar ratio of the compound phenazine with the structural formula (e) to the compound with the structural formula (f) is 1:2.
the preparation method of the compound with the structural formula (b) comprises the following steps: 1-bromo-3-buten-2-ol and perfluorohexylethylene are mixed in a molar ratio of 1:1, adding dibenzoyl peroxide and an ethanol aqueous solution into a reaction kettle, heating to 60 ℃, carrying out heating condensation reflux reaction, and after the reaction is finished, standing and separating to obtain the compound with the structural formula (b).
The nitroaniline with the structural formula (e) is 4-chloro-5-methyl-2-nitro-aniline.
Example 4
The electrochromic material and the preparation method thereof in this embodiment are basically the same as those in embodiment 1, and mainly differ in that the compound having the structural formula (b) is obtained by reacting 1-bromo-3-buten-2-ol with perfluorodecylene during the preparation process, and R1 is a perfluoroalkyl chain with 8 carbon atoms in the finally prepared electrochromic material.
As an alternative to examples 1-4, the compound of formula (d) may be replaced with one of 3-iodopropanol, 1-bromo-2-propanol, 3-bromo-1-propanol, 1-bromo-2-butanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-n-hexanol, 7-bromo-1-heptanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 11-bromo-1-undecanol, 12-bromo-1-dodecanol, 13-bromotridecan-1-ol, 14-bromotetradec-1-ol, 2-chloroethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, and 10-chloro-1-decanol to prepare electrochromic materials of corresponding chemical formula.
As an alternative to the technical solutions in examples 1 to 4, the nitroaniline with the structural formula (e) may be 4-chloro-2-nitroaniline, 5-ethoxy-4-fluoro-2-nitroaniline, 5-fluoro-2-nitroaniline, 4-fluoro-2-nitroaniline, 4,5-difluoro-2-nitroaniline, 4- (3-nitrophenyl) aniline, 5-methoxy-2-nitroaniline, 4-methoxy-5-methyl-2-nitroaniline, 4,5-dimethoxy-2-nitroaniline, 4-methoxy-2-nitroaniline, 4,5-diethoxy-2-nitroaniline, 4-ethoxy-5-fluoro-2-nitroaniline, 4-ethoxy-5-ethyl-2-nitroaniline, 4-ethoxy-2-nitroaniline, or 2-nitro-4-propoxyaniline, so as to prepare electrochromic materials with corresponding chemical structural formulas.
Application example
Referring to fig. 1 to 2, in an application example, the mobile terminal 100 is a smart phone. In other embodiments, the mobile terminal 100 may be a tablet, a palmtop, or the like. The mobile terminal 100 includes a housing assembly, an optical device 3, a circuit board, a battery, etc., the housing assembly includes a housing and an electrochromic cell module 21 disposed on the housing, the optical device 3, the circuit board and the battery are disposed in the housing assembly, the battery is connected to the circuit board and can supply power to the circuit board and the optical device 3, and the circuit board can be used to adjust the voltage of the electrochromic cell module 21. The housing comprises a front housing 1 provided with a display screen module 11 and a rear housing 2 departing from the display screen module 11, an inner cavity capable of bearing and accommodating components such as an optical device 3, a circuit board and a battery is defined between the front housing 1 and the rear housing 2, and the rear housing 2 is sometimes called as a rear cover, a rear housing or a battery cover. The rear case 2 may be made of a metal material such as aluminum alloy, magnesium alloy, stainless steel, etc., and the rear case 2 may be made of a non-metal material such as glass, ceramic, plastic, resin, etc. The rear shell 2 is provided with a through hole so that light can be incident on the optical device 3, and the size of the through hole is matched with the arrangement area range of the optical device. The electrochromic cell module 21 is fixedly connected to the through hole of the rear case 2 so that the electrochromic cell module 21 and the optical device 3 are disposed at positions corresponding to each other.
The optical device 3 may include one or more of a camera module, a flash, and a focus sensor. The camera module can be used for collecting images, such as photographing, video recording, video call and the like. The flash lamp can be used to the rear camera light filling to promote the shooting quality of rear camera. The focusing sensor can be used for focusing the camera module in the shooting process so as to improve the shooting quality of the camera module.
Referring to fig. 3, the electrochromic cell module 21 includes: a first substantially transparent conductive substrate; a second substantially transparent conductive substrate, the first and second conductive substrates being disposed in a spaced apart relationship; a seal member disposed substantially circumferentially between peripheral regions of the first and second electrically conductive substrates to sealingly bond oppositely disposed surfaces of the first and second electrically conductive substrates to each other and define a cavity; the cavity is filled with the electrochromic material prepared according to the above embodiment. The first conductive substrate is a glass substrate 211 plated with a transparent conductive film 214, the second conductive substrate is a glass substrate 212 plated with a conductive reflective layer 215, the transparent conductive film 214 and the conductive reflective layer 215 are electrically connected to corresponding electrodes, a sealed cavity 216 is formed on the glass substrate between the transparent conductive film 214 and the conductive reflective layer 215 by bonding with a sealing member epoxy resin 213, and the electrochromic material 217 is disposed in the sealed cavity 216. The transparent conductive film 214 is tin dioxide, indium tin oxide, fluorine-doped indium tin oxide, or aluminum-doped zinc oxide, and the resistance of the transparent conductive film 2 is preferably less than 25 ohms. The conductive reflective layer 215 is a layer of chromium, silver, aluminum, stainless steel or nickel, or an alloy layer of two or more of the above metal elements.
The optical device 3 and the electrochromic unit module 21 are arranged on the mobile terminal 100 in a facing manner, that is, the electrochromic unit module 21 covers the optical device 3; when the mobile terminal 100 does not start the camera function, the electrochromic cell module 21 is in a colored state, at this time, the light transmittance of the electrochromic cell module 21 is low, and the optical device 3 is shielded by the electrochromic cell module 21 and is not easy to be perceived, so that the overall appearance integrity of the mobile terminal is improved; furthermore, the color of the electrochromic unit module 21 after color change is matched with the appearance color of the rear shell, so that the visual aesthetic degree of the mobile terminal is further improved; when the mobile terminal 100 starts the camera function, the electrochromic cell module 21 responds quickly to make it in a fading state, and at this time, the light transmittance of the electrochromic cell module 21 is high, and the normal functional use of the optical device 3 is not affected.
Application example 1
Manufacturing an electrochromic unit module: a transparent ITO conducting layer plated on a glass substrate and a conductive reflecting layer plated with a silver film are bonded by epoxy resin, a pouring opening is left, and the epoxy resin is cured and molded at room temperature.
0.5g of the electrochromic material synthesized in example 1 was dissolved in 20ml of propylene carbonate, stirred uniformly and poured into the electrochromic unit module, and sealed with UV glue.
The electrochromic unit module is fixedly connected to the rear shell with the through hole, the rear shell is covered on the front shell containing the optical device, the circuit board, the battery and other parts, so that the whole smart phone is assembled, and the electrochromic unit module is arranged right opposite to the optical device.
Conventional performance tests were conducted on electrochromic cell modules, where the aging resistance tests were conducted in an aging resistant box, with ultraviolet lamp aging (280-400 nm), with the following results:
application example 2
Manufacturing an electrochromic unit module: a transparent conductive layer coated with ITO on a glass substrate and a conductive reflective layer coated with a silver film are bonded by epoxy resin, a pouring opening is left, and the epoxy resin is cured and molded at room temperature.
0.5g of the electrochromic material synthesized in example 1 was dissolved in 20ml of propylene carbonate, stirred uniformly and poured into the electrochromic unit module, and sealed with UV glue.
The electrochromic unit module is fixedly connected to the rear shell with the through hole, the rear shell is covered on the front shell containing optical devices, a circuit board, a battery and other parts, so that the complete smart phone is assembled, and the electrochromic unit module is arranged right opposite to the optical devices.
Conventional performance tests were conducted on electrochromic cell modules, where the aging resistance tests were conducted in an aging resistant box, with ultraviolet lamp aging (280-400 nm), with the following results:
| test items | Performance index |
| Transmittance in transparent state | 85.2％ |
| Transmittance in colored state | 7.9％ |
| Contrast ratio | 77 |
| Color change response time | 0.78s |
| Fade response time | 0.76s |
| Aging resistance time | >168h |
Application example 3
Manufacturing an electrochromic unit module: a transparent conductive layer coated with ITO on a glass substrate and a conductive reflective layer coated with a silver film are bonded by epoxy resin, a pouring opening is left, and the epoxy resin is cured and molded at room temperature.
0.5g of the electrochromic material synthesized in example 1 was dissolved in 20ml of propylene carbonate, stirred uniformly and poured into the above electrochromic cell module, and sealed with UV glue.
The electrochromic unit module is fixedly connected to the rear shell with the through hole, the rear shell is covered on the front shell containing optical devices, a circuit board, a battery and other parts, so that the complete smart phone is assembled, and the electrochromic unit module is arranged right opposite to the optical devices.
Conventional performance tests were conducted on electrochromic cell modules, where the aging resistance tests were conducted in an aging resistant box, with ultraviolet lamp aging (280-400 nm), with the following results:
application example 4
Manufacturing an electrochromic unit module: a transparent ITO conducting layer plated on a glass substrate and a conductive reflecting layer plated with a silver film are bonded by epoxy resin, a pouring opening is left, and the epoxy resin is cured and molded at room temperature.
0.5g of the electrochromic material synthesized in example 1 was dissolved in 20ml of propylene carbonate, stirred uniformly and poured into the electrochromic unit module, and sealed with UV glue.
The electrochromic unit module is fixedly connected to the rear shell with the through hole, the rear shell is covered on the front shell containing optical devices, a circuit board, a battery and other parts, so that the complete smart phone is assembled, and the electrochromic unit module is arranged right opposite to the optical devices.
Conventional performance tests were conducted on electrochromic cell modules, where the aging resistance tests were conducted in an aging resistant box, with ultraviolet lamp aging (280-400 nm), with the following results:
it can be seen that the present invention has considerable advantages over the currently used technology. The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.
Claims (9)
1. An electrochromic material, wherein the electrochromic material is an ion pair compound composed of a functional group containing a cathodic electrochromic function and a functional group containing an anodic electrochromic function, and the ion pair compound has a general chemical structure formula of formula (I):
in the formula:
R 1 is a perfluoroalkyl chain of 4 to 12 carbon atoms;
R 2 is an alkanyl radical having 2 to 16 carbon atoms;
R 3 is an alkanyl radical having 1 to 2 carbon atoms;
R 4 and R 5 The groups are the same or different and are one of H, cl, F, phenyl, methoxy, ethoxy and propoxy.
2. A method for preparing an electrochromic material according to claim 1, characterized in that it comprises the following steps:
s1: mixing 4,4' -bipyridine with a solvent according to a mass ratio of 1: 3-20, stirring and mixing uniformly, then adding a compound with a structural formula (b) to carry out a chemical reaction, controlling the reaction temperature to be 40-80 ℃ and the reaction time to be 2-144 h, thus obtaining a mixed solution A containing a bipyridine salt intermediate product with a structural formula (c);
s2: adding a compound with a structural formula (d) into the mixed solution A obtained in the step S1 to perform a chemical reaction, performing heating condensation reflux reaction at the temperature of 40-80 ℃, wherein the reaction time is 2-48 h, and performing crystallization separation to obtain a bipyridine salt compound with a structural formula (II);
s3: dissolving nitroaniline with the structural formula (e) in a hydrochloric acid solution, cooling to 0-10 ℃, then slowly adding a sodium nitrite solution, and carrying out diazotization reaction to obtain a reaction product with the structural formula (f); meanwhile, dissolving catechol into a sodium hydroxide solution to obtain catechol sodium salt; adding the reaction product with the structural formula (f) and sodium pyrocatechol salt into a sodium carbonate solution for coupling reaction, stopping the reaction when the alkalinity in the reaction materials is not reduced any more, and filtering to obtain a reaction product with the structural formula (g); adding the reaction product with the structural formula (g) into a proper amount of sodium hydroxide alkali liquor, uniformly stirring, adding zinc powder, carrying out reduction reaction, filtering to remove residues such as the zinc powder after the reaction is completed, adding hydrochloric acid at normal temperature for acidification, crystallizing, and filtering to obtain a compound with the structural formula (h); finally, reacting the compound with the structural formula (h) with o-phenylenediamine in a heating tube to obtain the phenazine derivative with the structural formula (i);
s4: mixing a phenazine derivative with a structural formula (i) and a solution consisting of sodium hydrosulfite, sodium carbonate and a small amount of water according to a mass ratio of 1: 4-40, stirring and mixing uniformly, then adding a compound with a structural formula (j) for chemical reaction, and carrying out heating condensation reflux reaction at the temperature of 40-80 ℃ for 2-48 h to obtain a mixed solution B containing a phenazine sodium salt compound with a structural formula (III); carrying out ion exchange on the mixed solution B and silver nitrate, and carrying out crystallization separation to obtain a phenazine silver salt compound with a structural formula (IV);
s5: the bipyridine salt compound of formula (II) obtained in step S2 and the phenazine silver salt compound of formula (IV) obtained in step S4 are mixed in a molar ratio of 1:1, adding the mixture into an ethanol solution, reacting to separate out silver halide precipitate, and after separating the precipitate, carrying out reduced pressure distillation on the upper layer liquid to obtain a target product with a structural formula (I);
in the formula:
R 1 is a perfluoroalkyl chain of 4 to 12 carbon atoms;
R 2 is an alkanyl radical having 2 to 16 carbon atoms;
R 3 is an alkanyl radical having 1 to 2 carbon atoms;
R 4 and R 5 The groups are the same or different and are one of H, cl, F, methyl, ethyl, phenyl, methoxy, ethoxy and propoxy.
3. The method of claim 2, wherein the molar ratio of the compound of formula (a) 4,4' -bipyridine to the compound of formula (b) is 1 to 1.2:1; the molar ratio of the compound with the structural formula (d) to the bipyridine salt intermediate product with the structural formula (c) is 1:1.
4. the method of claim 2, wherein in step S1, the solvent is one or more of tetrahydrofuran, acetonitrile, toluene, xylene, DMF, and ethyl acetate.
5. The method of preparing an electrochromic material according to claim 2, wherein the compound of formula (b) is prepared by: 1-bromo-3-buten-2-ol and perfluoroalkyl ethylene are mixed according to a molar ratio of 1:1, adding dibenzoyl peroxide and an ethanol aqueous solution into a reaction kettle, heating to 60-120 ℃, carrying out heating condensation reflux reaction, and standing and separating after the reaction is finished to obtain the compound with the structural formula (b).
6. The method of claim 5, wherein the perfluoroalkylethylene is one of perfluorobutylethylene, 1H, 2H-perfluoro-1-decene, perfluorohexylethylene, perfluorodecylethylene, and perfluorododecylethylene.
7. The method for preparing an electrochromic material according to claim 2, wherein the compound of formula (d) is one of 2-iodoethanol, 3-iodopropanol, 1-bromo-2-propanol, 3-bromo-1-propanol, 1-bromo-2-butanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-n-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 11-bromo-1-undecanol, 12-bromo-1-dodecanol, 13-bromotridecan-1-ol, 14-bromotetradec-1-ol, 16-bromohexadec-1-ol, 2-chloroethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, 10-chloro-1-decanol.
8. A housing assembly comprising a housing and an electrochromic cell module disposed on said housing, said electrochromic cell module comprising:
a first substantially transparent conductive substrate;
a second substantially transparent conductive substrate, the first and second conductive substrates being disposed in a spaced apart relationship and defining a cavity; and
the electrochromic material of claim 1 disposed in the cavity.
9. A mobile terminal, characterized in that the mobile terminal comprises a camera and the housing assembly of claim 8, the camera and the electrochromic cell module are arranged opposite to each other on the mobile terminal; when the mobile terminal does not start the camera shooting function, the electrochromic unit module is in a coloring state; and when the mobile terminal starts a camera shooting function, the electrochromic unit module is in a fading state.
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