CN101885821B - Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof - Google Patents
Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN101885821B CN101885821B CN2010102160628A CN201010216062A CN101885821B CN 101885821 B CN101885821 B CN 101885821B CN 2010102160628 A CN2010102160628 A CN 2010102160628A CN 201010216062 A CN201010216062 A CN 201010216062A CN 101885821 B CN101885821 B CN 101885821B
- Authority
- CN
- China
- Prior art keywords
- schiff bases
- type tri
- gathers
- conjugated type
- arylamine group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CC**1C=CCC1 Chemical compound CC**1C=CCC1 0.000 description 2
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a preparation method and application of conjugated triarylamine poly-Schiff base, in particular to a conjugated triarylamine poly-Schiff base as well as a preparation method and application thereof, aiming at solving the problems of low dissolubility in organic solvents, difficult processing as well as expensive raw materials and rigorous and complicated synthesis route required for light-emitting and displaying polymers, and difficult regulation and control of color change of the traditional poly-Schiff base. The method comprises the following steps: adding the organic solutions of dialdehyde compounds to N,N-di(4-amino-benzene)-N',N'-diphenyl-1,4-phenylenediamine in three times, making the mixture react for 10-12 hours at 160 DEG C under the condition of nitrogen protection, settling polymers, and extracting and drying to obtain the conjugated triarylamine poly-Schiff base. The conjugated triarylamine poly-Schiff base has the advantages of high temperature resistance and solubility in the organic solvents. Under the action of acidity or voltage, the color of the poly-Schiff bas changes reversibly.
Description
Technical field
The present invention relates to a kind of preparation method and application that gathers schiff bases.
Background technology
Get into the information age, organic electronic is learned and has been obtained swift and violent development as an emerging subject.Organic electronic combines with subjects such as organic chemistry, Materials science and is born a collection of type material with remarkable photoelectric properties, has contained numerous areas such as comprising display material, camouflage material, information storage material, sensing material and intelligent material.Gathering schiff bases and will shining flourishing vitality once introduce showing with sensory field of changing color resulting from acid and electrochromic performance all shows outstanding meliority and wide development application prospect in demonstration and sensory field.The existing schiff bases solvability in organic solvent of gathering is lower, is difficult to film forming processing, is that monomer can reduce the strong effect power between the polymer molecular chain effectively with three arylamine of propeller type, increases the solvability of polymkeric substance.Three arylamine are easy to form radical cation and demonstrate three arylamine that are different from neutral, therefore possess color tunable property; On the other hand; The synthetic raw material that needs costliness of common luminous or variable color polymkeric substance, harsh synthesis condition, and the present invention is through adding second monomer; Can regulate and control to gather the transformation region of schiff bases very easily, this is that other materials is difficult to realize with this method.
Summary of the invention
Goal of the invention of the present invention is low in order to solve the existing schiff bases solvability in organic solvent of gathering; Be difficult to processing; And common luminous demonstration base polymer needs expensive raw material with harsh loaded down with trivial details synthetic route and have the problem that colour-change is not easy to regulate and control, and provides a kind of conjugated type tri-arylamine group to gather preparation method and application that schiff bases, conjugated type tri-arylamine group are gathered schiff bases.
The structural formula that conjugated type tri-arylamine group of the present invention gathers schiff bases is following:
The preparation method that the conjugated type tri-arylamine group gathers schiff bases is following: one, the dialdehyde-based compound is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of according to 1: 2～6 volume ratio toluene and N,N-DIMETHYLACETAMIDE; Two, with N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, under temperature is 160 ℃, the condition of nitrogen protection, reacts 10～14 hours; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get the conjugated type tri-arylamine group and gather schiff bases, its structural formula is following:
Described conjugated type tri-arylamine group gathers schiff bases and causes sensing material, hole mobile material, third order non-linear optical material, anti-fake material, camouflage material, automobile rearview mirror material or display material as electrochromic material, photochromic material, changing color resulting from acid material, acid.
Conjugated type tri-arylamine group of the present invention gathers schiff bases and has overcome and gather the shortcoming that Schiff's base is difficult to be dissolved in common organic solvents in the past; The conjugated type tri-arylamine group gathers schiff bases by N; N-two (4-amino-benzene)-N '; N '-phenylbenzene-1; The reaction of 4-phenylenediamine and dialdehyde-based compound makes, and three arylamine structures are wherein utilized the non-coplanarity of three arylamine to reduce polymer molecule piling up to increase solubility property that the conjugated type tri-arylamine group gathers schiff bases in solution and made the conjugated type tri-arylamine group gather schiff bases to be dissolved in the part organic solvent.
The conjugated type tri-arylamine group gathers formation C=N double bond structure in the schiff bases, and two keys are connecting phenyl ring, form big conjugated structure; This is that other is unexistent like amido linkage and imide bond blocking-up type structure; Electronic cloud can transmit in very long molecular chain, and the character of polymkeric substance embodies the combination synergistic effect, and photoabsorption takes place the material with this structure easily; After acid doping or oxidation, cause color to change, and going the reversible change phenomenon of back generation of mixing.As the main raw in the changing color resulting from acid device, the conjugated type tri-arylamine group gathers schiff bases and has very big advantage, and changing color resulting from acid is because electron-withdrawing group (C=N) and electron-donating group (fluorine-triphenylamine structure) all contain the nitrogen-atoms responsive to proton.The electronic structure of very malleable suction of the intrusion of alien species, electron-donating group; Changed the structure of whole molecular chain; Thereby changed the character of the absorption luminous energy of molecule; Reach the photoswitch effect thereby have good changing color resulting from acid characteristic, the potential application prospect is arranged at aspects such as information storage and sensings.
The conjugated type tri-arylamine group gathers in the electrochromic property practical application of schiff bases and has following meliority: (1) has good electrochemical redox reversibility, through still keeping reversible after more than ten times to the tens times oxidation reduction cycle; (2) time of response of colour-change fast, after making alive, can rapid variable color within 0.5 second; (3) change in color is a reversible; (4) colour-change is highly sensitive; (5) higher cycle life is arranged; (6) certain storing memory function is arranged; Before and after response; Can stably remain on the state after virgin state or the variable color, can keep after the variable color several months to several years, color can remain unchanged and reaches half a year behind electrochromism and changing color resulting from acid in this experiment; (7) better chemical stability is arranged, under the normal temperature and pressure, maybe stable existence in the air.
Description of drawings
Fig. 1 is that embodiment four gained conjugated type tri-arylamine groups gather the infrared spectrum of schiff bases; Fig. 2 is that embodiment four gained conjugated type tri-arylamine groups gather the proton magnetic spectrum figure of schiff bases; Fig. 3 is that embodiment four gained conjugated type tri-arylamine groups gather the sensing variable color spectrogram in the changing color resulting from acid device of schiff bases;
expression is with the original absorbancy curve that gathers schiff bases solution of dissolved in chloroform among the figure;
expression is with the absorbancy curve after schiff bases solution adds acid that gathers of dissolved in chloroform, and
expression is with the absorbancy curve after schiff bases solution adds alkali again that gathers of dissolved in chloroform; Fig. 4 is that embodiment four gained conjugated type tri-arylamine groups gather the electrochromism cyclic voltammetric spectrogram of schiff bases; Fig. 5 is the variable color spectrogram when the conjugated type tri-arylamine group gathers schiff bases generation redox in electrochromic device in the embodiment four; Fig. 6 is that embodiment four gained conjugated type tri-arylamine groups gather the thermogravimetric analysis spectrogram of schiff bases; Fig. 7 is that embodiment five gained conjugated type tri-arylamine groups gather the infrared spectrum of schiff bases; Fig. 8 is that embodiment five gained conjugated type tri-arylamine groups gather the proton magnetic spectrum figure of schiff bases; Fig. 9 is that embodiment five gained conjugated type tri-arylamine groups gather the sensing variable color spectrogram in the changing color resulting from acid device of schiff bases;
expression is with the original absorbancy curve that gathers schiff bases solution of dissolved in chloroform among the figure, and
expression is with the absorbancy curve after schiff bases solution adds acid that gathers of dissolved in chloroform; Figure 10 is that embodiment five gained conjugated type tri-arylamine groups gather the electrochromism cyclic voltammetric spectrogram of schiff bases; Figure 11 is the variable color spectrogram when the conjugated type tri-arylamine group gathers schiff bases generation redox in electrochromic device in the embodiment five; Figure 12 is that embodiment five gained conjugated type tri-arylamine groups gather the thermogravimetric analysis spectrogram of schiff bases; Figure 13 is that embodiment six gained conjugated type tri-arylamine groups gather the infrared spectrum of schiff bases; Figure 14 is that embodiment six gained conjugated type tri-arylamine groups gather the proton magnetic spectrum figure of schiff bases; Figure 15 is that embodiment six gained conjugated type tri-arylamine groups gather the sensing variable color spectrogram in the changing color resulting from acid device of schiff bases;
expression is with the original absorbancy curve that gathers schiff bases solution of dissolved in chloroform among the figure, and
expression is with the absorbancy curve after schiff bases solution adds acid that gathers of dissolved in chloroform; Figure 16 is that embodiment six gained conjugated type tri-arylamine groups gather the electrochromism cyclic voltammetric spectrogram of schiff bases; Figure 17 is the variable color spectrogram when the conjugated type tri-arylamine group gathers schiff bases generation redox in electrochromic device in the embodiment six; Figure 18 is that embodiment six gained conjugated type tri-arylamine groups gather the thermogravimetric analysis spectrogram of schiff bases; Figure 19 is that embodiment seven gained conjugated type tri-arylamine groups gather the infrared spectrum of schiff bases; Figure 20 is that embodiment seven gained conjugated type tri-arylamine groups gather the proton magnetic spectrum figure of schiff bases; Figure 21 is that embodiment seven gained conjugated type tri-arylamine groups gather the sensing variable color spectrogram in the changing color resulting from acid device of schiff bases;
expression is with the original absorbancy curve that gathers schiff bases solution of dissolved in chloroform among the figure, and
expression is with the absorbancy curve after schiff bases solution adds acid that gathers of dissolved in chloroform; Figure 22 is that embodiment seven gained conjugated type tri-arylamine groups gather the electrochromism cyclic voltammetric spectrogram of schiff bases; Figure 23 is the variable color spectrogram when the conjugated type tri-arylamine group gathers schiff bases generation redox in electrochromic device in the embodiment seven; Figure 24 is that embodiment seven gained conjugated type tri-arylamine groups gather the thermogravimetric analysis spectrogram of schiff bases; Figure 25 is that embodiment eight gained conjugated type tri-arylamine groups gather the infrared spectrum of schiff bases; Figure 26 is that embodiment eight gained conjugated type tri-arylamine groups gather the proton magnetic spectrum figure of schiff bases; Figure 27 is that embodiment eight gained conjugated type tri-arylamine groups gather the sensing variable color spectrogram in the changing color resulting from acid device of schiff bases;
expression is with the original absorbancy curve that gathers schiff bases solution of dissolved in chloroform among the figure;
expression is with the absorbancy curve after schiff bases solution adds acid that gathers of dissolved in chloroform, and
expression is with the absorbancy curve after schiff bases solution adds alkali again that gathers of dissolved in chloroform; Figure 28 is that embodiment eight gained conjugated type tri-arylamine groups gather the electrochromism cyclic voltammetric spectrogram of schiff bases; Figure 29 is the variable color spectrogram when the conjugated type tri-arylamine group gathers schiff bases generation redox in electrochromic device in the embodiment eight; Figure 30 is that embodiment eight gained conjugated type tri-arylamine groups gather the thermogravimetric analysis spectrogram of schiff bases;
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the monomeric replacement of the different aldehyde with reactant of arbitrary combination between each embodiment.
Embodiment one: it is following that the conjugated type tri-arylamine group gathers the structural formula of schiff bases in this embodiment:
N is a positive integer in
formula, and R does
Embodiment two: to gather the preparation method of schiff bases following for the conjugated type tri-arylamine group in this embodiment: one, the dialdehyde-based compound is dissolved in the organic solvent; Obtain mixed solution, organic solvent is made up of according to 1: 2～6 volume ratio toluene and N,N-DIMETHYLACETAMIDE; Two, with N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, under temperature is 160 ℃, the condition of nitrogen protection, reacts 10～14 hours; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get the conjugated type tri-arylamine group and gather schiff bases, its structural formula is following:
N in this embodiment, N-two (4-amido benzene)-N ', N '-phenylbenzene-1, the compound method of 4-phenylenediamine is following: one, 20ml YLENE and 30ml DMSO 99.8MIN. are mixed, obtain mixed solvent; Two, 14.9995g4-triaminotriphenyl amine, 14ml p-fluoronitrobenzene, 8.7757g salt of wormwood and 0.5g copper powder catalyst are added in the solvent, stirring and refluxing 24h under 160 ℃ condition uses the HCL dilute solution repetitive scrubbing of concentration as 6.47mol/L then then; And be washed till filtrating with zero(ppm) water and be neutral, N is used in twice vacuum-drying; The dinethylformamide recrystallization obtains N, N-two (4-oil of mirbane)-N '; N '-phenylbenzene-1, the 4-phenylenediamine; Three, with N, N-two (4-oil of mirbane)-N ', N '-phenylbenzene-1, the 4-phenylenediamine is dissolved in N; Dinethylformamide is put into the high pressure hydrogen reaction kettle then, adds the Pb/C catalyzer, is that 7MPa, temperature are under 70 ℃ the condition at hydrogen; Reaction 48h removes by filter the Pb/C catalyzer, pours into then in the deionized water, obtains white flocks; Suction filtration at 50 ℃ of dry 24h, is used the ethyl alcohol recrystallization purifying, vacuum-drying then again; Promptly get N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1,4-phenylenediamine.
Embodiment three: the conjugated type tri-arylamine group gathers schiff bases and causes sensing material, hole mobile material, third order non-linear optical material, anti-fake material, camouflage material, automobile rearview mirror material or display material as electrochromic material, photochromic material, changing color resulting from acid material, acid in this embodiment.
Embodiment four: to gather the preparation method of schiff bases following for the conjugated type tri-arylamine group in this embodiment: one, the 0.1361g terephthalic aldehyde is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of 5ml toluene and 15ml N,N-DIMETHYLACETAMIDE; Two, with 0.4434g N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, is reaction 11 hours under 160 ℃, the condition of nitrogen protection in temperature; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get 0.3315g conjugated type tri-arylamine group and gather schiff bases (vermilion red powder, productive rate are 57.2%).Reaction formula is following:
Fig. 1 explanation is at wave number 1620cm
-1The place exists gathers the C=N stretching vibration characteristic peak of schiff bases.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Fig. 2 explanation at chemical shift 8.6 places.
Fig. 3 explains with the solution that gathers schiff bases with dissolved in chloroform has absorption peak at 455nm and 320nm place; After being blown into acid gas, the color of primary solution and has disappeared at the absorption peak at 455nm place from the yellow to the blueness; To above-mentioned conjugated type tri-arylamine group after mixing with acid gather be blown into ammonia in the schiff bases solution after, solution begins to occur absorption peak again at 455nm.Explain after original solution is blown into acid gas the changing color resulting from acid phenomenon has taken place, be blown into the ammonia solution colour again and revert to virgin state, changing color resulting from acid takes place after adding acid more again, be blown into ammonia again and return to virgin state again.
Fig. 4 explains that this embodiment obtains gather Schiff's base under impressed voltage, its electronic structure changes, and has formed the polymkeric substance of oxidation state; 3 peaks are arranged in 0.3～1.2V; That is to say that gathering schiff bases has three kinds of oxidation state forms, and their color is different.
What Fig. 5 explained this embodiment gathers schiff bases under the 0v current potential; At 440nm and 330nm place strong absorption peak is arranged,, slowly weaken at the absorption peak of 440nm along with the increase of current potential; Peak in the 540nm back raises with the rising of current potential gradually; The color of polymkeric substance deepens gradually, and therefore explanation is under externally-applied potential, and this gathers schiff bases generation metachromatism.
Fig. 6 explains that the schiff bases of gathering of this embodiment reaches 464 ℃ in temperature and locates weightlessly 10%, locates weightlessly 40% at 574 ℃, and therefore gathering schiff bases has great high-temperature resistant.
Embodiment five: to gather the preparation method of schiff bases following for the conjugated type tri-arylamine group in this embodiment: one, the 0.1396g isophthalic aldehyde is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of 5ml toluene and 15ml N,N-DIMETHYLACETAMIDE; Two, with 0.4435g N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, is reaction 11 hours under 160 ℃, the condition of nitrogen protection in temperature; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get 0.3458g conjugated type tri-arylamine group and gather schiff bases (yellow powder, productive rate are 59.3%).Reaction formula is following:
Fig. 7 explanation is at wave number 1620cm
-1The place exists gathers the C=N stretching vibration characteristic peak of schiff bases.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Fig. 8 explanation at chemical shift 8.6 and 8.4 places.
Fig. 9 explains that the solution that gathers schiff bases with dissolved in chloroform has absorption peak at 430nm and 320nm place; After in primary solution, being blown into acid gas, the color of primary solution is from the yellow to the purple, and the absorption peak at the 430nm place has disappeared; Disappearing about 430nm and occurring after absorption peak explanation original solution is blown into acid gas again the changing color resulting from acid phenomenon having taken place.
Figure 10 explains that this embodiment obtains gather Schiff's base under impressed voltage, its electronic structure changes, and has formed the polymkeric substance of oxidation state; 3 peaks are arranged in 0.3～1.2V; That is to say that gathering schiff bases has three kinds of oxidation state forms, and their color is different.
What Figure 11 explained this embodiment gathers schiff bases under the 0v current potential; At 440nm and 320nm place strong absorption peak is arranged,, slowly weaken at the absorption peak of 440nm along with the increase of current potential; Peak in the 490nm back raises with the rising of current potential gradually; The color of polymkeric substance deepens gradually, and therefore explanation is under externally-applied potential, and this gathers schiff bases generation metachromatism.
Figure 12 explains that the schiff bases of gathering of this embodiment reaches 466 ℃ in temperature and locates weightlessly 10%, locates weightlessly 40% at 591 ℃, and therefore gathering schiff bases has great high-temperature resistant.
Embodiment six: to gather the preparation method of schiff bases following for the conjugated type tri-arylamine group in this embodiment: one, the 0.1385g Phthalyldicarboxaldehyde is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of 5ml toluene and 15ml N,N-DIMETHYLACETAMIDE; Two, with 0.4451gN, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, is reaction 12 hours under 160 ℃, the condition of nitrogen protection in temperature; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get 0.1926g conjugated type tri-arylamine group and gather schiff bases (brown ceramic powder, productive rate are 33.0%).Reaction formula is following:
Figure 13 explanation is at wave number 1620cm
-1The place exists gathers the C=N stretching vibration characteristic peak of schiff bases.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Figure 14 explanation at chemical shift 8.014 places.
Figure 15 explains that the solution that gathers schiff bases with dissolved in chloroform has absorption peak at the 320nm place; After in primary solution, being blown into acid gas, to light yellow, the solution after sour matter is mixed has absorption peak at the 325nm place to the color of primary solution, and blue shift takes place from yellow, and original solution after being blown into acid gas again the changing color resulting from acid phenomenon has taken place.
Figure 16 explains that this embodiment obtains gather Schiff's base under impressed voltage, its electronic structure changes, and has formed the polymkeric substance of oxidation state; 1 peak is arranged in 0.3～0.7V; That is to say that gathering schiff bases has a kind of oxidation state form, and their color is different.
What Figure 17 explained this embodiment gathers the increase of schiff bases along with current potential, and the absorption peak more than 320nm slowly weakens, and therefore explanation is under externally-applied potential, and this gathers schiff bases generation metachromatism.
Figure 18 explains that the schiff bases of gathering of this embodiment reaches 422 ℃ in temperature and locates weightlessly 10%, locates weightlessly 40% at 629 ℃, and therefore gathering schiff bases has great high-temperature resistant.
Embodiment seven: to gather the preparation method of schiff bases following for the conjugated type tri-arylamine group in this embodiment: one, 0.1855g dialdehyde-based triphenylamine is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of 5ml toluene and 15ml N,N-DIMETHYLACETAMIDE; Two, with 0.2722gN, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, is reaction 12 hours under 160 ℃, the condition of nitrogen protection in temperature; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get 0.3313g conjugated type tri-arylamine group and gather schiff bases (yellow powder, productive rate are 72.4%).Reaction formula is following:
Figure 19 explanation is at wave number 1620cm
-1The place exists gathers the C=N stretching vibration characteristic peak of schiff bases.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Figure 20 explanation at chemical shift 8.44 places.
Figure 21 explains that the solution that gathers schiff bases with dissolved in chloroform has absorption peak at 455nm and 320nm place; After in primary solution, being blown into acid gas, the color of primary solution is from the yellow to the scarlet, and the absorption peak at the 455nm place disappears, and generates new absorption peak at the 570nm place; Slacken and new absorption peak occurs at the absorption peak of 455nm, explain after original solution is blown into acid gas the changing color resulting from acid phenomenon has taken place at the 570nm place.
Figure 22 explains that this embodiment obtains gather Schiff's base under impressed voltage, its electronic structure changes, and has formed the polymkeric substance of oxidation state; 2 peaks are arranged in 0.3～1.2V; That is to say that gathering schiff bases has two kinds of oxidation state forms, and their color is different.
What Figure 23 explained this embodiment gathers the variation of schiff bases along with current potential; Absorption peak more than 400nm slowly weakens, and raises gradually with the rising of current potential at the peak of 480nm back, and the color of polymkeric substance deepens gradually; Therefore explanation is under externally-applied potential, and this gathers schiff bases generation metachromatism.
Figure 24 explains that the schiff bases of gathering of this embodiment reaches 476 ℃ in temperature and locates weightlessly 10%, locates weightlessly 40% at 576 ℃, so the schiff bases of gathering of this embodiment has great high-temperature resistant.
Embodiment eight: to gather the preparation method of schiff bases following for the conjugated type tri-arylamine group in this embodiment: one, 0.1170g thiophene dialdehyde is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of 5ml toluene and 15ml N,N-DIMETHYLACETAMIDE; Two, with 0.3693g N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, is reaction 12 hours under 160 ℃, the condition of nitrogen protection in temperature; With the cold methanol polymkeric substance that settles out, used the methyl alcohol extracting polymer again 72 hours, dry 12h then; Promptly get 0.3889gg conjugated type tri-arylamine group and gather schiff bases (vermilion red powder, productive rate are 80.0%).Reaction formula is following:
Figure 25 explanation is at wave number 1620cm
-1The place exists gathers the C=N stretching vibration characteristic peak of schiff bases.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Figure 26 explanation at chemical shift 8.64 places.
Figure 27 explains that the solution that gathers schiff bases with dissolved in chloroform has absorption peak at 500nm and 340nm place; After in primary solution, being blown into acid gas, the color of primary solution is from the redness to the blueness, and the absorption peak at the 500nm place disappears; To above-mentioned conjugated type tri-arylamine group after mixing with acid gather be blown into ammonia in the schiff bases solution after, solution begins to occur absorption peak again at 500nm.Disappearing about 500nm and occurring after absorption peak explanation original solution is blown into acid gas again the changing color resulting from acid phenomenon having taken place, be blown into the ammonia solution colour again and revert to virgin state, changing color resulting from acid takes place again after adding acid again, be blown into ammonia again and return to virgin state again.
Figure 28 explains that this embodiment obtains gather Schiff's base under impressed voltage, its electronic structure changes, and has formed the polymkeric substance of oxidation state; 3 peaks are arranged in 0.3～1.2V; That is to say that gathering schiff bases has three kinds of oxidation state forms, and their color is different.
What Figure 29 explained this embodiment gathers the variation of schiff bases along with current potential, raises gradually with the rising of current potential at the peak of 570nm back, and the color of polymkeric substance deepens gradually, and therefore explanation is under externally-applied potential, and this gathers schiff bases generation metachromatism.
Figure 30 explains that the schiff bases of gathering of this embodiment reaches 450 ℃ in temperature and locates weightlessly 10%, locates weightlessly 40% at 565 ℃, and therefore gathering schiff bases has great high-temperature resistant.
Claims (3)
1. the conjugated type tri-arylamine group gathers schiff bases, it is characterized in that the structural formula that said conjugated type tri-arylamine group gathers schiff bases is following:
N is a positive integer in
formula, and R does
wherein
R " is (CH
2)
pCH
3, p is 0～8, or
Wherein R ' is H or OCH
3, m is 1～8;
The conjugated type tri-arylamine group gathers schiff bases and prepares by following preparation method: one, the dialdehyde-based compound is dissolved in the organic solvent, obtains mixed solution, organic solvent is made up of according to 1: 2～6 volume ratio toluene and N,N-DIMETHYLACETAMIDE; Two, with N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, under temperature is 160 ℃, the condition of nitrogen protection, reacts 10～14 hours; Then with the cold methanol polymkeric substance that settles out, use the methyl alcohol extracting polymer again 72 hours, dry 12h promptly gets the conjugated type tri-arylamine group and gathers schiff bases;
Wherein the dialdehyde-based compound described in the step 1 does
2. the conjugated type tri-arylamine group gathers the preparation method of schiff bases; It is following to it is characterized in that with the phenylenediamine being that raw material conjugated type tri-arylamine group gathers the preparation method of schiff bases: one, the dialdehyde-based compound is dissolved in the organic solvent; Obtain mixed solution, organic solvent is made up of according to 1: 2～6 volume ratio toluene and N,N-DIMETHYLACETAMIDE; Two, with N, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The 4-phenylenediamine joins in the reactor drum, places oil bath pan to be heated to 90 ℃ reactor drum then, divides after the mixed solution that again step 1 is prepared is divided into 3 parts to join in the reactor drum for 3 times; Dialdehyde-based compound and N in the reactor drum, N-two (4-amino-benzene)-N ', N '-phenylbenzene-1; The mol ratio of 4-phenylenediamine is 0.9～1.1: 1, and the temperature in the question response device rises to 160 ℃, under temperature is 160 ℃, the condition of nitrogen protection, reacts 10～14 hours; Then with the cold methanol polymkeric substance that settles out; Use the methyl alcohol extracting polymer again 72 hours, dry 12h promptly gets the conjugated type tri-arylamine group and gathers schiff bases, and its structural formula is following:
N is a positive integer in
formula, and R does
R " is (CH
2)
pCH
3, p is 0～8, or
Wherein R ' is H or OCH
3, m is 1～8; Dialdehyde-based compound described in the step 1 does
3. conjugated type tri-arylamine group as claimed in claim 1 gathers the application of schiff bases as photovaltaic material, it is characterized in that described conjugated type tri-arylamine group gathers schiff bases and causes sensing material, hole mobile material, third order non-linear optical material, anti-fake material, camouflage material, automobile rearview mirror material or display material as electrochromic material, photochromic material, changing color resulting from acid material, acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102160628A CN101885821B (en) | 2010-07-02 | 2010-07-02 | Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102160628A CN101885821B (en) | 2010-07-02 | 2010-07-02 | Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101885821A CN101885821A (en) | 2010-11-17 |
| CN101885821B true CN101885821B (en) | 2012-01-18 |
Family
ID=43071930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102160628A Expired - Fee Related CN101885821B (en) | 2010-07-02 | 2010-07-02 | Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101885821B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304226A (en) * | 2011-05-27 | 2012-01-04 | 吉林大学 | Polyazomethine hole transport material and preparation method thereof |
| NL2012451B1 (en) * | 2014-03-17 | 2016-01-08 | Univ Delft Tech | Small azomethine molecule. |
| RU2657084C2 (en) * | 2016-12-01 | 2018-06-08 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Photosensitizer for solar cells |
| CN109734930B (en) * | 2019-01-23 | 2021-03-30 | 福州大学 | Preparation method and application of acid-responsive color-changing material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3373077A (en) * | 1963-06-07 | 1968-03-12 | Monsanto Res Corp | Soluble and fusible, heat resistant, chelate polymers |
| JPS4939000A (en) * | 1972-08-18 | 1974-04-11 |
-
2010
- 2010-07-02 CN CN2010102160628A patent/CN101885821B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101885821A (en) | 2010-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yam et al. | Highlights on the recent advances in gold chemistry—a photophysical perspective | |
| Santra et al. | Electrochemical polymerization of triphenylamine end-capped dendron: Electrochromic and electrofluorochromic switching behaviors | |
| Mi et al. | Donor–π-bridge–acceptor fluorescent polymers based on thiophene and triphenylamine derivatives as solution processable electrochromic materials | |
| Usluer et al. | A novel high‐contrast ratio electrochromic material from spiro [cyclododecane‐1, 9′‐fluorene] bicarbazole | |
| Sun et al. | Electroactive (A3+ B2)-type hyperbranched polyimides with highly stable and multistage electrochromic behaviors | |
| CN101293961B (en) | Electrochromic polymeric compounds, preparing method and application thereof | |
| CN101885821B (en) | Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof | |
| Wang et al. | Photovoltaic performance of long-chain poly (triphenylamine-phenothiazine) dyes with a tunable π-bridge for dye-sensitized solar cells | |
| Du et al. | Donor-π-bridge-acceptor type polymeric materials with pendant electron-withdrawing groups for electrochromic applications | |
| Zhang et al. | Electrochromic and electrofluorochromic bifunctional materials for dual-mode devices based on ladder-like polysilsesquioxanes containing triarylamine | |
| CN112430314B (en) | Electrochromic polymer containing indacenodithiophene structure, preparation method, polymer film and application | |
| Hu et al. | Electrochemical and electrochromic properties of polymers based on 2, 5-di (2-thienyl)-1H-pyrrole and different phenothiazine units | |
| CN101885820B (en) | Triarylated amine polyschiff base, preparation method thereof taking triphenylamine as raw material and application | |
| Hsiao et al. | Redox-active and electrochromic polymers from triarylamine end-capped, 2, 7-bis (diphenylamino) naphthalene-cored dicarboxamides | |
| Gao et al. | Novel polyamides containing asymmetric diamine designed and synthesized towards electrochromic and resistance memory device | |
| Anizaim et al. | Insight into the impact of the substituent modification on the photovoltaic performance of ferrocenyl chalcones based DSSCs | |
| CN101885819B (en) | Conjugated poly-Schiff base as well as method for preparing same by using aromatic diamine monomers as raw materials and application thereof | |
| CN101880388A (en) | Poly-schiff base, preparation method thereby by taking aromatic diamine monomer as raw material and applications thereof | |
| EP3609976B1 (en) | Organic photochromic dye and uses thereof for dye sensitized solar cells | |
| CN102585218B (en) | Polyaniline derivative, preparation method of reductive poly Schiff base of polyaniline derivative and application of polyaniline derivative | |
| CN110713493A (en) | Electrochemical polymerization preparation and application of triphenylamine derivative conjugated polymer material | |
| CN101885822B (en) | Soluble conjugate-type polymeric schiff base, preparation method and application thereof | |
| CN104788356A (en) | Pyrrole-containing triphenylamine conjugated schiff base compound, and preparation method and application thereof | |
| Umeki et al. | Acid–Base Responsive Photoelectric Conversion of a Hydroxyazobenzene-appended Bipyridine–Copper Complex System | |
| CN112430312B (en) | Electrochromic polymer containing carbazole structure, preparation method, polymer film and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20101117 Assignee: Daqing New Century Fine Chemicals Co., Ltd. Assignor: Heilongjiang University Contract record no.: 2014230000119 Denomination of invention: Conjugated triarylamine poly-Schiff base as well as preparation method and application thereof Granted publication date: 20120118 License type: Exclusive License Record date: 20140416 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120118 Termination date: 20200702 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |