CN101885822B - Soluble conjugate-type polymeric schiff base, preparation method and application thereof - Google Patents
Soluble conjugate-type polymeric schiff base, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a soluble conjugate-type polymeric schiff base, a preparation method and the application thereof, in particular to the preparation method and the application of the soluble conjugate-type polymeric schiff base, aiming at solving the problems that the existing soluble conjugate-type polymeric schiff base has low dissolubility in organic solvent and is difficult to process, and the common luminous display polymers need expensive raw materials as well as strict and complicated synthetic route and can not easily adjust and control the color change. The method comprises the following steps of: adding organic solution of dialdehyde compound into N, N' -diphenyl-N, N' - 2 (4-phenylamine) biphenyl diamine for three times; carrying out reflux under the condition of nitrogen protection at 50-170 DEG C; precipitating polymer, extracting and filtering; carrying out Soxhlet extraction and drying; and finally, obtaining the soluble conjugate-type polymeric schiff base. The soluble conjugate-type polymeric schiff base resists high temperature, and can be dissolved in organic solvent. Under the action of acidity or voltage, the reversible color change of the soluble conjugate-type polymeric schiff base occurs.
Description
Technical field
The present invention relates to a kind of preparation method and application of poly-schiff bases.
Background technology
Enter 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.Poly-schiff bases with changing color resulting from acid and electrochromic property will shine flourishing vitality once introducing demonstration and sensory field, all shows outstanding superiority and wide development application prospect in demonstration and sensory field.Existing poly-schiff bases solvability in organic solvent 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 present the color that is different from middle condition, and because the second monomeric adding, acting in conjunction makes poly-schiff bases possess color tunable; 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 by adding second monomer, can synthesize poly-schiff bases very easily, and the color change interval of adjustable poly-schiff bases, this is that other materials is difficult to realize with this method.
Summary of the invention
The objective of the invention is in order to solve existing poly-schiff bases solvability in organic solvent low, be difficult to processing, and common luminous demonstration base polymer needs the loaded down with trivial details synthetic route of expensive raw material and harshness and has the problem that colour-change is not easy to regulate and control, and provides a kind of solvable conjugated type to gather the preparation method and the application of schiff bases, the poly-schiff bases of solvable conjugated type.
The structural formula of the poly-schiff bases of the solvable conjugated type of the present invention is as follows:
The preparation method of the poly-schiff bases of above-mentioned solvable conjugated type is as follows: one, the dialdehyde-based compound is dissolved in the organic solvent, obtains mixed solution, the ratio of dialdehyde-based compound and organic solvent is 0.1g～0.5g: 10ml; Two; with N; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and organic solvent join in the reactor according to the ratio of 0.1g～0.5g: 10ml; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; dialdehyde-based compound and N in the reactor; N '-phenylbenzene-N; the mol ratio of N '-two (4-aniline) benzidine is 0.98～1.1: 1, and the add-on of lithium chloride is dialdehyde-based compound and N, N '-phenylbenzene-N; 0～50% of N '-two (4-aniline) benzidine total mass; then at 50 ℃～170 ℃; refluxed under the condition of nitrogen protection 10 hours, then with the cold methanol polymkeric substance that settles out, suction filtration; Soxhlet was extracted 10～36 hours; oven dry promptly gets the poly-schiff bases of solvable conjugated type, and its structural formula is as follows:
The poly-schiff bases of described solvable conjugated type is as the application of photoelectric material, and the poly-schiff bases of described solvable conjugated type 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.
The poly-schiff bases solvability in organic solvent of existing solvable conjugated type is lower, be difficult to film forming processing, three arylamine with propeller type are that monomer can reduce the strong effect power between the polymer molecular chain effectively, increase the solvability of polymkeric substance, three arylamine are easy to form radical cation and present the color that is different from middle condition, and because the second monomeric adding, acting in conjunction makes the poly-schiff bases of solvable conjugated type possess color tunable; 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 by adding second monomer, the synthesis of soluble conjugated type gathers schiff bases and regulates and control the color change interval that solvable conjugated type gathers schiff bases very easily, and this is that other materials is difficult to realize with this method.
The poly-schiff bases of solvable conjugated type of the present invention is dissolved in organic solvent, owing in the poly-schiff bases of the solvable conjugated type of tri-arylamine group, formed the conjugated electrons cloud of electron delocalization wide range, material photoabsorption with this structure can change along with the change of structural unit: because the difference of dialdehyde-based compound, the position of the absorption peak of the poly-schiff bases of solvable conjugated type changes between 400nm～500nm.Under the effect of acidity or voltage, the poly-schiff bases of solvable conjugated type generates doping attitude polymkeric substance or radical cation, thereby causes the poly-schiff bases color of solvable conjugated type to produce reversible change phenomenon.
The poly-schiff bases of solvable conjugated type that contains tri-arylamine group has very high resistance and high temperature resistance property, and general under the atmosphere of nitrogen, decomposition temperature is adapted at using in the device more than 400 ℃.
Have following superiority in the electrochromic property practical application of the poly-schiff bases of solvable conjugated type: (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, the poly-schiff bases color behind electrochromism and changing color resulting from acid of solvable in this experiment conjugated type can remain unchanged and reach half a year; (7) before and after the material variable color better chemical stability is arranged, under the normal temperature and pressure, may stable existence in the air.
Description of drawings
Fig. 1 is the infrared spectrum of the poly-schiff bases of the solvable conjugated type of gained in the embodiment eight; Fig. 2 is the proton magnetic spectrum figure of the poly-schiff bases of the solvable conjugated type of embodiment eight gained; Fig. 3 is the thermogravimetric analysis spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment eight gained; Fig. 4 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment eight gained; Fig. 5 is the sensing variable color spectrogram in the changing color resulting from acid device of the poly-schiff bases of the solvable conjugated type of embodiment eight gained, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved; Fig. 6 is the variable color spectrogram when solvable conjugated type gathers schiff bases generation redox in electrochromic device in the embodiment eight; Fig. 7 is the infrared spectrum of the poly-schiff bases of the solvable conjugated type of embodiment nine gained; Fig. 8 is the proton magnetic spectrum figure of the poly-schiff bases of the solvable conjugated type of embodiment nine gained; Fig. 9 is the thermogravimetric analysis spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment nine gained; Figure 10 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment nine gained; Figure 11 is the poly-sensing variable color spectrograms of schiff bases in the changing color resulting from acid device of embodiment nine solvable conjugated types, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved; Figure 12 is the variable color spectrogram when solvable conjugated type gathers schiff bases generation redox in electrochromic device in the embodiment nine; Figure 13 is the infrared spectrum of the poly-schiff bases of the solvable conjugated type of embodiment ten gained; Figure 14 is the proton magnetic spectrum figure of the poly-schiff bases of the solvable conjugated type of embodiment ten gained; Figure 15 is the thermogravimetric analysis spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment ten gained; Figure 16 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment ten gained; Figure 17 is the poly-sensing variable color spectrogram of schiff bases in the changing color resulting from acid device of solvable conjugated type in the embodiment ten, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved; Figure 18 is the variable color spectrogram when solvable conjugated type gathers schiff bases generation redox in electrochromic device in the embodiment ten; Figure 19 is the infrared spectrum of the poly-schiff bases of the solvable conjugated type of embodiment 11 gained; Figure 20 is the proton magnetic spectrum figure of the poly-schiff bases of the solvable conjugated type of embodiment 11 gained; Figure 21 is the thermogravimetric analysis spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment 11 gained; Figure 22 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of the solvable conjugated type of embodiment 11 gained; Figure 23 is the poly-sensing variable color spectrogram of schiff bases in the changing color resulting from acid device of solvable conjugated type in the embodiment 11, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of the solvable conjugated type of chloroform dissolved; Figure 24 is the variable color spectrogram when solvable conjugated type gathers schiff bases generation redox in electrochromic device in the embodiment 11.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprise between each embodiment arbitrary combination and with the replacement of the different dialdehyde of diamine reactant.
Embodiment one: the structural formula of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment:
Embodiment two: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the dialdehyde-based compound is dissolved in the organic solvent, obtains mixed solution, the ratio of dialdehyde-based compound and organic solvent is 0.1g～0.5g: 10ml; Two; with N; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and organic solvent join in the reactor according to the ratio of 0.1g～0.5g: 10ml; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; dialdehyde-based compound and N in the reactor; N '-phenylbenzene-N; the mol ratio of N '-two (4-aniline) benzidine is 0.98～1.1: 1, and the add-on of lithium chloride is dialdehyde-based compound and N, N '-phenylbenzene-N; 0～50% of N '-two (4-aniline) benzidine total mass; then at 50 ℃～170 ℃; refluxed under the condition of nitrogen protection 10 hours, then with the cold methanol polymkeric substance that settles out, suction filtration; Soxhlet was extracted 10～36 hours; oven dry promptly gets the poly-schiff bases of solvable conjugated type, and its structural formula is as follows:
N is a positive integer in the formula, and R is
Organic solvent described in the step 2 is by N, and dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone and toluene are according to 3～10: 1 volume ratio is formed.
Embodiment three: what present embodiment and embodiment two were different is that the organic solvent described in step 1 and the step 2 is by N, dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone and dimethylbenzene are according to 3～10: 1 volume ratio is formed.Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two are different be the organic solvent described in step 1 and the step 2 be N-Methyl pyrrolidone, HMPA or N-Methyl pyrrolidone and HMPA according to 3～10: 1 volume ratio is formed.Other is identical with embodiment two.
Embodiment five: present embodiment and embodiment two are different is dialdehyde-based compound and N in the reactor in the step 2, N '-phenylbenzene-N, and the mol ratio of N '-two (4-aniline) benzidine is 1: 1.Other is identical with embodiment two.
Embodiment six: present embodiment and embodiment two are different is to reflux 10 hours under 170 ℃, the condition of nitrogen protection in the step 2.Other is identical with embodiment two.
Embodiment seven: the poly-schiff bases of solvable conjugated type is as the application of photoelectric material in the present embodiment, and the poly-schiff bases of described solvable conjugated type 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.
Embodiment eight: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, 0.229g dialdehyde-based triphenylamine is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518g N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, add lithium chloride again, divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times, the add-on of lithium chloride is dialdehyde-based triphenylamine and N, N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass refluxed 10 hours under 160 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get the poly-schiff bases of solvable conjugated type, productive rate 88.86%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and toluene.
Fig. 1 explanation is at wave number 1620cm
-1There is the C=N stretching vibration characteristic peak of the poly-schiff bases of solvable conjugated type in the place.
There is the characteristic peak of hydrogen on the HC=N of the poly-schiff bases of solvable conjugated type in Fig. 2 explanation at chemical shift 8.44 places.
Fig. 3 illustrates that the poly-schiff bases of solvable conjugated type reaches 100 ℃ in temperature and locates weightlessness 5%, locates weightlessness 50% at 579 ℃, and therefore the poly-schiff bases of solvable conjugated type has great high-temperature resistant.
Fig. 4 illustrate poly-Schiff's base that present embodiment obtains under impressed voltage, its electronic structure changes, and that is to say, the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 2 peaks, illustrates that this polymkeric substance has 2 kinds of states of oxidation.
Fig. 5 illustrates that the solution with the poly-schiff bases of the solvable conjugated type of chloroform dissolved has absorption peak at the 426nm place, absorbs purple light, and polymkeric substance is shown as yellow-green colour.After being blown into acid gas, absorption peak (absorption yellow green light) is arranged at the 546nm place, be shown as purple; The color of primary solution is changed to purple from yellow-green colour; Be blown into ammonia in the above-mentioned poly-schiff bases solution of the solvable conjugated type of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 426nm.Illustrate 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.Illustrate that the poly-schiff bases of solvable conjugated type has soda acid response reversibility.
Fig. 6 illustrates that the absorption peak of the poly-schiff bases of solvable conjugated type changes along with the variation of current potential.Absorption peak is arranged about 460nm when not powering up, and the peak position red shift gradually with the rising of current potential illustrates that the color of polymkeric substance deepens gradually, and this solvable conjugated type gathers schiff bases generation metachromatism.
Embodiment nine: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g o-phthalaldehyde(OPA) is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518g N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, add lithium chloride again, divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times, the add-on of lithium chloride is o-phthalaldehyde(OPA) and N, N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass refluxed 10 hours under 160 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get the poly-schiff bases of solvable conjugated type, productive rate 78%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and toluene.
Fig. 7 explanation is at wave number 1639cm
-1There is the C=N stretching vibration characteristic peak of the poly-schiff bases of solvable conjugated type in the place.
There is the characteristic peak of hydrogen on the HC=N of the poly-schiff bases of solvable conjugated type in Fig. 8 explanation at chemical shift 7.9 places.
Fig. 9 illustrates that the poly-schiff bases of solvable conjugated type reaches 370 ℃ in temperature and locates weightlessness 5%, locates weightlessness 45% at 612 ℃, and therefore the poly-schiff bases of solvable conjugated type has great high-temperature resistant.
Figure 10 illustrate poly-Schiff's base that present embodiment obtains under impressed voltage, its electronic structure changes, and that is to say, the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 1 peak, illustrates that this polymkeric substance has a kind of state of oxidation.
Figure 11 illustrates that the solution with the poly-schiff bases of the solvable conjugated type of chloroform dissolved has absorption peak at the 440nm place, absorbs purple light, and polymkeric substance is shown as yellow-green colour.After being blown into acid gas, absorption peak (absorption yellow green light) is arranged at the 506nm place, be shown as red-violet colour; The color of primary solution changes to red-violet colour from yellow-green colour; Be blown into ammonia in the above-mentioned poly-schiff bases solution of the solvable conjugated type of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 440nm.Illustrate 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.Illustrate that the poly-schiff bases of solvable conjugated type has soda acid response reversibility.
Figure 12 illustrates the variation of the poly-schiff bases of solvable conjugated type along with current potential, raises gradually with the rising of current potential at the peak of 450nm back, and the color of polymkeric substance deepens gradually, and this solvable conjugated type gathers schiff bases generation metachromatism.
Embodiment ten: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g m-terephthal aldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518g N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, add lithium chloride again, divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times, the add-on of lithium chloride is m-terephthal aldehyde and N, N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass refluxed 10 hours under 160 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get the poly-schiff bases of solvable conjugated type, productive rate 85.6%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and toluene.
Figure 13 explanation is at wave number 1627cm
-1There is the C=N stretching vibration characteristic peak of the poly-schiff bases of solvable conjugated type in the place.
There is the characteristic peak of hydrogen on the H C=N of the poly-schiff bases of solvable conjugated type in Figure 14 explanation at chemical shift 8.6 places.
Figure 15 illustrates that the poly-schiff bases of solvable conjugated type reaches 480 ℃ in temperature and locates weightlessness 5%, locates weightlessness 45% at 634 ℃, and therefore the poly-schiff bases of solvable conjugated type has great high-temperature resistant.
Figure 16 illustrate poly-Schiff's base that present embodiment obtains under impressed voltage, its electronic structure changes, and that is to say, the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 2 peaks, illustrates that this polymkeric substance has three kinds of redox structures.
Figure 17 illustrates that the solution with the poly-schiff bases of the solvable conjugated type of chloroform dissolved has absorption peak at the 402nm place, absorbs purple light, and polymkeric substance is shown as yellow-green colour.After being blown into acid gas, absorption peak (absorption yellow green light) is arranged at the 529nm place, be shown as red-violet colour; The color of primary solution changes to red-violet colour from yellow-green colour; Be blown into ammonia in the above-mentioned poly-schiff bases solution of the solvable conjugated type of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 402nm.Illustrate 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.
The absorption peak of the poly-schiff bases of solvable conjugated type of Figure 18 explanation changes along with the variation of current potential.Peak in the 530nm back raises gradually with the rising of current potential, and the color of polymkeric substance deepens gradually, and this solvable conjugated type gathers schiff bases generation electrochromism phenomenon.
Embodiment 11: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g terephthalaldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518gN, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, add lithium chloride again, divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times, the add-on of lithium chloride is terephthalaldehyde and N, N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass refluxed 10 hours under 160 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get the poly-schiff bases of solvable conjugated type, productive rate 88.2%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and toluene.
Figure 19 explanation is at wave number 1623cm
-1There is the C=N stretching vibration characteristic peak of the poly-schiff bases of solvable conjugated type in the place.
There is the characteristic peak of hydrogen on the HC=N of the poly-schiff bases of solvable conjugated type in Figure 20 explanation at chemical shift 8.59 places.
Figure 21 illustrates that the poly-schiff bases of solvable conjugated type reaches 468 ℃ in temperature and locates weightlessness 5%, locates weightlessness 30% at 620 ℃, and therefore the poly-schiff bases of solvable conjugated type has great high-temperature resistant.
Figure 22 illustrate poly-Schiff's base that present embodiment obtains under impressed voltage, its electronic structure changes, and that is to say, the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 2 peaks, illustrates that this polymkeric substance has 2 kinds of states of oxidation.
Figure 23 illustrates that the solution with the poly-schiff bases of the solvable conjugated type of chloroform dissolved has absorption peak at the 445nm place, absorbs purple light, and polymkeric substance is shown as yellow.After being blown into acid gas, absorption peak (absorbing orange light) is arranged at the 634nm place, be shown as turquoise; The color of primary solution is from the yellow to the turquoise; Be blown into ammonia in the above-mentioned poly-schiff bases solution of the solvable conjugated type of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 445nm.Illustrate 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.Illustrate that the poly-schiff bases of solvable conjugated type has soda acid response reversibility.
Figure 24 illustrates the variation along with current potential of the poly-schiff bases of solvable conjugated type, and absorption peak changes along with the variation of current potential.Peak at the 455nm place reduces gradually with the rising of 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 this solvable conjugated type gathers schiff bases generation electrochromism phenomenon.
Embodiment 12: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, 0.229g dialdehyde-based triphenylamine is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518gN, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, divide 3 times after the mixed solution that step 1 is obtained is divided into 3 parts then and add, and reflux 10 hours under 140 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get and gather schiff bases, productive rate 87.64%; Organic solvent described in step 1 and the step 2 is by N, and N '-N,N-DIMETHYLACETAMIDE and dimethylbenzene are formed according to 3: 1 volume ratio.
Embodiment 13: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g o-phthalaldehyde(OPA) is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518gN, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, divide 3 times after the mixed solution that step 1 is obtained is divided into 3 parts then and add, and reflux 10 hours under 140 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get and gather schiff bases, productive rate 75.4%; Organic solvent described in step 1 and the step 2 is by N, and N '-N,N-DIMETHYLACETAMIDE and dimethylbenzene are formed according to 3: 1 volume ratio.
Embodiment 14: the preparation method of poly-schiff bases is as follows in the present embodiment: one, the 0.134g m-terephthal aldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518g N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, divide 3 times after the mixed solution that step 1 is obtained is divided into 3 parts then and add, and reflux 10 hours under 140 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get and gather schiff bases, productive rate 86.5%; Organic solvent described in step 1 and the step 2 is by N, and N '-N,N-DIMETHYLACETAMIDE and dimethylbenzene are formed according to 3: 1 volume ratio.
Embodiment 15: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g terephthalaldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.518gN, N '-phenylbenzene-N, N '-two (4-aniline) benzidine and 20ml organic solvent join in the reactor, divide 3 times after the mixed solution that step 1 is obtained is divided into 3 parts then and add, and reflux 10 hours under 140 ℃, the condition of nitrogen protection then, with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 24 hours, oven dry, promptly get and gather schiff bases, productive rate 87.4%; Organic solvent described in step 1 and the step 2 is by N, and N '-N,N-DIMETHYLACETAMIDE and dimethylbenzene are formed according to 3: 1 volume ratio.
Embodiment 16: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, 0.229g dialdehyde-based triphenylamine is dissolved in the 20mlN-crassitude ketone solvent, obtains mixed solution; Two, with 0.518g N; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and 20mlN-crassitude ketone solvent join in the reactor; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; the add-on of lithium chloride is dialdehyde-based triphenylamine and N; N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass, reaction 10 hours under 170 ℃, the condition of nitrogen protection then; with the cold methanol polymkeric substance that settles out; suction filtration, Soxhlet was extracted 24 hours, oven dry; promptly get and gather schiff bases, productive rate 82.3%.
Embodiment 17: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g o-phthalaldehyde(OPA) is dissolved in the 20mlN-crassitude ketone solvent, obtains mixed solution; Two, with 0.518gN; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and 20mlN-crassitude ketone solvent join in the reactor; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; the add-on of lithium chloride is o-phthalaldehyde(OPA) and N; N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass, reaction 10 hours under 170 ℃, the condition of nitrogen protection then; with the cold methanol polymkeric substance that settles out; suction filtration, Soxhlet was extracted 24 hours, oven dry; promptly get and gather schiff bases, productive rate 79.1%.
Embodiment 18: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g m-terephthal aldehyde is dissolved in the 20mlN-crassitude ketone solvent, obtains mixed solution; Two, with 0.518g N; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and 20mlN-crassitude ketone solvent join in the reactor; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; the add-on of lithium chloride is m-terephthal aldehyde and N; N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass, reaction 10 hours under 170 ℃, the condition of nitrogen protection then; with the cold methanol polymkeric substance that settles out; suction filtration, Soxhlet was extracted 24 hours, oven dry; promptly get and gather schiff bases, productive rate 85.4%.
Embodiment 19: the preparation method of the poly-schiff bases of solvable conjugated type is as follows in the present embodiment: one, the 0.134g terephthalaldehyde is dissolved in the 20mlN-crassitude ketone solvent, obtains mixed solution; Two, with 0.518g N; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and 20mlN-crassitude ketone solvent join in the reactor; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; the add-on of lithium chloride is terephthalaldehyde and N; N '-phenylbenzene-N, 50% of N '-two (4-aniline) benzidine total mass, reaction 10 hours under 170 ℃, the condition of nitrogen protection then; with the cold methanol polymkeric substance that settles out; suction filtration, Soxhlet was extracted 24 hours, oven dry; promptly get and gather schiff bases, productive rate 88.2%.
Claims (5)
1. solvable conjugated type gathers schiff bases, it is characterized in that the structural formula of the poly-schiff bases of described solvable conjugated type is as follows:
2. the described solvable conjugated type of claim 1 gathers the preparation method of schiff bases, the preparation method who it is characterized in that the poly-schiff bases of solvable conjugated type is as follows: one, the dialdehyde-based compound is dissolved in the organic solvent, obtain mixed solution, the ratio of dialdehyde-based compound and organic solvent is 0.1g～0.5g: 10ml; Two; with N; N '-phenylbenzene-N; N '-two (4-aniline) benzidine and organic solvent join in the reactor according to the ratio of 0.1g～0.5g: 10ml; add lithium chloride again; divide after the mixed solution that step 1 is obtained is divided into 3 parts then and add for 3 times; dialdehyde-based compound and N in the reactor; N '-phenylbenzene-N; the mol ratio of N '-two (4-aniline) benzidine is 0.98～1.1: 1, and the add-on of lithium chloride is dialdehyde-based compound and N, N '-phenylbenzene-N; 0～50% of N '-two (4-aniline) benzidine total mass; then at 50 ℃～170 ℃; refluxed under the condition of nitrogen protection 10 hours, then with the cold methanol polymkeric substance that settles out, suction filtration; Soxhlet was extracted 10～36 hours; oven dry promptly gets the poly-schiff bases of solvable conjugated type, and its structural formula is as follows:
Dialdehyde-based compound described in the step 1 is
, wherein R " is (CH
2)
pCH
3, p is 0, or
Wherein R ' is H or OCH
3, m is 1; Organic solvent described in step 1 and the step 2 is by N, and dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone and toluene or dimethylbenzene are according to 3～10: 1 volume ratio is formed.
3. according to the preparation method of the poly-schiff bases of the described solvable conjugated type of claim 2, it is characterized in that interior dialdehyde-based compound of reactor and N in the step 2, N '-phenylbenzene-N, the mol ratio of N '-two (4-aniline) benzidine is 1: 1.
4. according to the preparation method of the poly-schiff bases of the described solvable conjugated type of claim 2, it is characterized in that in the step 2 under 170 ℃, the condition of nitrogen protection, refluxing 10 hours.
5. the poly-schiff bases of solvable conjugated type as claimed in claim 1 is characterized in that as the application of photoelectric material the poly-schiff bases of described solvable conjugated type 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.
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