CN101885819B - Conjugated poly-Schiff base as well as method for preparing same by using aromatic diamine monomers as raw materials and application thereof - Google Patents
Conjugated poly-Schiff base as well as method for preparing same by using aromatic diamine monomers as raw materials and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method and application of conjugated poly-Schiff base, in particular to a conjugated poly-Schiff base as well as a method for preparing the same by using aromatic diamine monomers as raw materials 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 conjugated poly-Schiff base. The method comprises the following steps: adding the organic solutions of dialdehyde compounds to N,N'-di(alpha-naphthyl)-N,N'-di(4-aniline) biphenyl diamine in three times, reflowing the mixture at 50-170 DEG C under the condition of nitrogen protection, settling polymers and carrying out pumping filtration, Soxhlet extraction and drying to obtain the conjugated poly-Schiff base. The conjugated poly-Schiff base in the invention has the advantages of high temperature resistance and solubility in the organic solvents. Under the action of acidity or voltage, the color of the conjugated poly-Schiff base changes reversibly.
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.The poly-schiff bases of conjugated type 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.The poly-schiff bases solvability in organic solvent of existing conjugated type 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 the poly-schiff bases of 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, can synthesize the poly-schiff bases of conjugated type very easily, and the color change interval of the poly-schiff bases of adjustable conjugated type, 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 the poly-schiff bases solvability in organic solvent of existing conjugated type 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 conjugated type to gather schiff bases, has been the preparation method and the application of the poly-schiff bases of raw material conjugated type with the aromatic diamine monomers.
The structural formula of the poly-schiff bases of conjugated type of the present invention is as follows:
Described preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers: 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 '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-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, and N '-two (α-Nai Ji)-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 conjugated type, and its structural formula is as follows:
The poly-schiff bases of above-mentioned conjugated type is characterized in that as the application of photoelectric material the poly-schiff bases of described 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 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, have the surely property write of environment, and because the second monomeric adding, acting in conjunction makes the poly-schiff bases of 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 conjugate type gathers schiff bases and regulates and control the color change interval that 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 conjugated type of the present invention is dissolved in organic solvent, owing in the poly-schiff bases of tri-arylamine group conjugated type, 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 conjugated type changes between 400nm～500nm.Under the effect of acidity or voltage, the poly-schiff bases of conjugated type generates doping attitude polymkeric substance or radical cation, thereby causes the poly-schiff bases color of conjugated type to produce reversible change phenomenon.
The poly-schiff bases of 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 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, color can remain unchanged and reaches more than half a year behind electrochromism and changing color resulting from acid in this experiment; (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 gained conjugated type in the embodiment eight; Fig. 2 is the proton magnetic spectrum figure of the poly-schiff bases of embodiment eight gained conjugated types; Fig. 3 is the thermogravimetric analysis spectrogram of the poly-schiff bases of embodiment eight gained conjugated types; Fig. 4 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of embodiment eight gained conjugated types; Fig. 5 is the sensing variable color spectrogram in the changing color resulting from acid device of the poly-schiff bases of embodiment eight gained conjugated types, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of chloroform dissolved conjugated type,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of chloroform dissolved conjugated type, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of chloroform dissolved conjugated type; Fig. 6 is the variable color spectrogram when 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 embodiment nine gained conjugated types; Fig. 8 is the proton magnetic spectrum figure of the poly-schiff bases of embodiment nine gained conjugated types; Fig. 9 is the thermogravimetric analysis spectrogram of the poly-schiff bases of embodiment nine gained conjugated types; Figure 10 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of embodiment nine gained conjugated types; Figure 11 is the poly-sensing variable color spectrograms of schiff bases in the changing color resulting from acid device of embodiment nine conjugated types, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of chloroform dissolved conjugated type,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of chloroform dissolved conjugated type, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of chloroform dissolved conjugated type; Figure 12 is the variable color spectrogram when 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 embodiment ten gained conjugated types; Figure 14 is the proton magnetic spectrum figure of the poly-schiff bases of embodiment ten gained conjugated types; Figure 15 is the thermogravimetric analysis spectrogram of the poly-schiff bases of embodiment ten gained conjugated types; Figure 16 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of embodiment ten gained conjugated types; Figure 17 is the poly-sensing variable color spectrogram of schiff bases in the changing color resulting from acid device of conjugated type in the embodiment ten, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of chloroform dissolved conjugated type,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of chloroform dissolved conjugated type, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of chloroform dissolved conjugated type; Figure 18 is the variable color spectrogram when 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 embodiment 11 gained conjugated types; Figure 20 is the proton magnetic spectrum figure of the poly-schiff bases of embodiment 11 gained conjugated types; Figure 21 is the thermogravimetric analysis spectrogram of the poly-schiff bases of embodiment 11 gained conjugated types; Figure 22 is the electrochromism cyclic voltammetric spectrogram of the poly-schiff bases of embodiment 11 gained conjugated types; Figure 23 is the poly-sensing variable color spectrogram of schiff bases in the changing color resulting from acid device of conjugated type in the embodiment 11, among the figure
The expression original absorbancy curve of the poly-schiff bases solution of chloroform dissolved conjugated type,
Expression adds absorbancy curve after the acid with the poly-schiff bases solution of chloroform dissolved conjugated type, represents
Add the absorbancy curve that adds again after the acid behind the alkali with the poly-schiff bases solution of chloroform dissolved conjugated type; Figure 24 is the variable color spectrogram when 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 comprises arbitrary combination and and the monomeric replacement of diamines polymeric dialdehyde-based between each embodiment.
Embodiment one: the structural formula of the poly-schiff bases of conjugated type is as follows in the present embodiment:
Embodiment two: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: 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 '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-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, and N '-two (α-Nai Ji)-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 conjugated type, and its structural formula is as follows:
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 '-two (Alpha-Naphthyl)-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 conjugated type is characterized in that as the application of photoelectric material the poly-schiff bases of described 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 in the present embodiment.
Embodiment eight: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, 0.229g dialdehyde-based triphenylamine is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 160 ℃, refluxed 10 hours under the condition of nitrogen protection, then with the cold methanol polymkeric substance that settles out, suction filtration, Soxhlet was extracted 10 hours, oven dry, promptly get the poly-schiff bases of conjugated type, productive rate 89.3%; 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 poly-schiff bases in the place.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Fig. 2 explanation at chemical shift 8.39 places.
Fig. 3 illustrates that poly-schiff bases reaches 458 ℃ in temperature and locates weightlessness 5%, locates weightlessness 45% at 604 ℃, and therefore poly-schiff bases 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 with the solution with the poly-schiff bases of chloroform dissolved has absorption peak at the 422nm place, absorbs purple light, and polymkeric substance is shown as yellow-green colour.After being blown into acid gas, absorption peak is arranged, absorb yellow green light, and be shown as purple at the 566nm place; The color of primary solution is from the yellow-green colour to the purple; Be blown into ammonia in the above-mentioned poly-schiff bases solution of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 422nm.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.
Fig. 6 illustrates that the absorption peak of poly-schiff bases changes along with the variation of current potential.Peak in the 500nm back raises gradually with the rising of current potential, and the color of polymkeric substance deepens gradually, this poly-schiff bases generation electrochromism phenomenon.
Embodiment nine: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g o-phthalaldehyde(OPA) is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 160 ℃, refluxed 10 hours under 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 conjugated type, productive rate 77.6%; 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.
Fig. 7 explanation is at wave number 1606cm
-1There is the C=N stretching vibration characteristic peak of poly-schiff bases in the place.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Fig. 8 explanation at chemical shift 8.04 places.
Fig. 9 illustrates that poly-schiff bases reaches 218 ℃ in temperature and locates weightlessness 5%, locates weightlessness 40% at 621 ℃, and therefore poly-schiff bases 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 2 peaks, illustrates that this polymkeric substance has 2 kinds of states of oxidation.
Figure 11 illustrates with the solution with the poly-schiff bases of chloroform dissolved has absorption peak at the 452nm place, absorbs purple light, and polymkeric substance is shown as yellow.After being blown into acid gas, absorption peak is arranged, absorb yellow green light, and be shown as red-violet colour at the 515nm place; The color of primary solution is from the yellow to the red-violet colour; Be blown into ammonia in the above-mentioned poly-schiff bases solution of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 452nm.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.
Figure 12 illustrates that the absorption peak of poly-schiff bases changes along with the variation of current potential.Peak in the 500nm back raises gradually with the rising of current potential, and the color of polymkeric substance deepens gradually, this poly-schiff bases generation electrochromism phenomenon.
Embodiment ten: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g m-terephthal aldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two; with 0.542g N; N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 160 ℃; refluxed 10 hours under 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 conjugated type, productive rate 85.3%. 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 1622cm
-1There is the C=N stretching vibration characteristic peak of poly-schiff bases in the place.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Figure 14 explanation at chemical shift 8.57 places.
Figure 15 illustrates that poly-schiff bases reaches 244 ℃ in temperature and locates weightlessness 5%, locates weightlessness 40% at 600 ℃, and therefore poly-schiff bases 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 0mA is an oxidation peak, contains 3 peaks, illustrates that this polymkeric substance has three kinds of states of oxidation.
Figure 17 illustrates with the solution with the poly-schiff bases of chloroform dissolved has absorption peak at the 409nm place, absorbs purple light, and polymkeric substance is shown as yellow-green colour.After being blown into acid gas, absorption peak is arranged, absorb yellow green light, and be shown as red-violet colour at the 528nm place; The color of primary solution is from the yellow-green colour to the red-violet colour; Be blown into ammonia in the above-mentioned poly-schiff bases solution of conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 409nm.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.
Figure 18 illustrates that the absorption peak of poly-schiff bases changes along with the variation of current potential.Peak in the 500nm back raises gradually with the rising of current potential, and the color of polymkeric substance deepens gradually, and this poly-schiff bases generation power transformation causes the look phenomenon.
Embodiment 11: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g terephthalaldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 160 ℃, refluxed 10 hours under 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 conjugated type, productive rate 88.4%; Organic solvent described in step 1 and the step 2 is by N, and N '-N,N-DIMETHYLACETAMIDE and toluene are formed according to 3: 1 volume ratio.
Figure 19 explanation is at wave number 1620cm
-1There is the C=N stretching vibration characteristic peak of poly-schiff bases in the place.
There is the characteristic peak of hydrogen on the HC=N that gathers schiff bases in Figure 20 explanation at chemical shift 8.52 places.
Figure 21 illustrates that poly-schiff bases reaches 363 ℃ in temperature and locates weightlessness 5%, locates weightlessness 30% at 597 ℃, and therefore poly-schiff bases 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 1 peak, illustrates that this polymkeric substance has a kind of state of oxidation.
Figure 23 illustrates with the solution with the poly-schiff bases of chloroform dissolved has absorption peak at the 430nm place, absorbs purple light, and polymkeric substance is shown as yellow.After being blown into acid gas, absorption peak is arranged, absorb orange light, and be shown as turquoise at the 582nm place; 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 conjugated type tri-arylamine group after mixing with acid after, solution begins to occur absorption peak again at 430nm.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.
Figure 24 illustrates that the absorption peak of poly-schiff bases changes along with the variation of current potential.Peak in the 570nm back raises gradually with the rising of current potential, and the color of polymkeric substance deepens gradually, this poly-schiff bases generation electrochromism phenomenon.
Embodiment 12: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, 0.229g dialdehyde-based triphenylamine is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 140 ℃, refluxed 10 hours under 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 conjugated type, productive rate 86.6%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and dimethylbenzene.
Embodiment 13: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g o-phthalaldehyde(OPA) is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 140 ℃, refluxed 10 hours under 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 conjugated type, productive rate 76.3%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and dimethylbenzene.
Embodiment 14: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g m-terephthal aldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-N, 50% of N ' two (4-aniline) benzidine total mass is then at 140 ℃, refluxed 10 hours under 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 conjugated type, productive rate 86.0%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and dimethylbenzene.
Embodiment 15: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g terephthalaldehyde is dissolved in the 20ml organic solvent, obtains mixed solution; Two, with 0.542g N, N '-two (Alpha-Naphthyl)-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, 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 conjugated type, productive rate 89.8%; Organic solvent described in step 1 and the step 2 is made up of according to 3: 1 volume ratio N,N-dimethylacetamide and dimethylbenzene.
Embodiment 16: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, 0.229g dialdehyde-based triphenylamine is dissolved in the 20mlN-methyl-2-pyrrolidone, obtains mixed solution; Two; with 0.542g N; N '-two (Alpha-Naphthyl)-N; N '-two (4-aniline) benzidine and 20mlN-methyl-2-pyrrolidone 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 '-two (Alpha-Naphthyl)-N, 50% of N '-two (4-aniline) benzidine total mass is then at 170 ℃; refluxed 10 hours under 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 conjugated type, productive rate 88.3%.
Embodiment 17: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g o-phthalaldehyde(OPA) is dissolved in the 20mlN-methyl-2-pyrrolidone, obtains mixed solution; Two, with 0.542g N; N '-two (Alpha-Naphthyl)-N; N '-two (4-aniline) benzidine and 20mlN-methyl-2-pyrrolidone 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 170 ℃, the condition of nitrogen protection then; 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 conjugated type, productive rate 75.7%.
Embodiment 18: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g m-terephthal aldehyde is dissolved in the 20mlN-methyl-2-pyrrolidone, obtains mixed solution; Two, with 0.542g N; N '-two (Alpha-Naphthyl)-N; N '-two (4-aniline) benzidine and 20mlN-methyl-2-pyrrolidone 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 170 ℃, the condition of nitrogen protection then; 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 conjugated type, productive rate 85.2%.
Embodiment 19: the preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers in the present embodiment: one, the 0.134g terephthalaldehyde is dissolved in the 20mlN-methyl-2-pyrrolidone, obtains mixed solution; Two, with 0.542gN; N '-two (Alpha-Naphthyl)-N; N '-two (4-aniline) benzidine and 20mlN-methyl-2-pyrrolidone 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 170 ℃, the condition of nitrogen protection then; 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 conjugated type, productive rate 88.8%.
Claims (5)
1. conjugated type gathers schiff bases, it is characterized in that the structural formula of the poly-schiff bases of described conjugated type is as follows:
Wherein R " is (CH
2)
pCH
3, p is 0, or
2. be the preparation method of the poly-schiff bases of raw material conjugated type with the aromatic diamine monomers, it is characterized in that described preparation method for the poly-schiff bases of raw material conjugated type is as follows with the aromatic diamine monomers: 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 '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-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 '-two (Alpha-Naphthyl)-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 conjugated type, and its structural formula is as follows:
, wherein R " is (CH
2)
pCH
3, p is 0, or
Wherein R ' is H, and 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 claim 2 is the preparation method that the raw material conjugated type gathers schiff bases with the aromatic diamine monomers, it is characterized in that interior dialdehyde-based compound of reactor and N in the step 2, N '-two (Alpha-Naphthyl)-N, the mol ratio of N '-two (4-aniline) benzidine is 1: 1.
4. according to the described preparation method who take the aromatic diamine monomers as the poly-schiff bases of raw material 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 conjugated type as claimed in claim 1 is characterized in that as the application of photoelectric material the poly-schiff bases of described 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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