CN102584600A - Polyaniline derivative, preparation method of reduced polySchiff base thereof and application of polyaniline derivative - Google Patents
Polyaniline derivative, preparation method of reduced polySchiff base thereof and application of polyaniline derivative Download PDFInfo
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Abstract
The invention discloses a polyaniline derivative, a preparation method of reduced polySchiff base thereof and an application of the polyaniline derivative, which relate to a polyaniline material and a preparation method and an application thereof and are used for solving the technical problem of low dissolubility in an organic solvent and difficulty in processing into a film existing in the conventional polyaniline. The structural formula of the polyaniline derivative disclosed by the invention is shown in the specifications. The preparation method comprises the following steps of: adding conjugate polySchiff base, a solvent and sodium borohydride into a three-neck flask; raising the temperature to 10-70 DEG C, stirring and refluxing for 10-72 hours; cooling and pouring into methanol; and filtering and drying to obtain the polyaniline derivative. The polyaniline derivative is applied as a photoelectric material, and comprises an electrochromic material, a fluorescent sensing material, an acid-based sensing material, a hole transport material, a three-order nonlinear material, an anti-counterfeiting material, a camouflage material, an automobile rearview mirror material or a display material.
Description
Technical field
The present invention relates to polyaniline material and preparation method and application.
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.Polyaniline and verivate thereof with electrochromic property all show outstanding meliority and wide development application prospect in demonstration and sensory field.Existing polyaniline solvability in organic solvent is lower, is difficult to use the solution method film forming, and is mostly to link to each other with the N atom between phenyl ring and phenyl ring, and the structure kind is limited, function singleness.
Summary of the invention
The present invention be to solve existing polyaniline structure and function singleness, solvability is low in organic solvent, is difficult to process film forming technical problem, and preparation method that polyaniline derivative and its reduction gather schiff bases and its application is provided.
The structural formula of polyaniline derivative of the present invention is following:
N is a positive integer in
formula, and Ar is
The preparation method that the reduction of above-mentioned polyaniline derivative gathers schiff bases carries out according to the following steps:
One, the mass volume ratio that gathers schiff bases and solvent by conjugated type is that to gather in the schiff bases mole of C=N key and Peng Qinghuana be 1: 3～10 to take by weighing conjugated type and gather schiff bases, solvent and Peng Qinghuana for 1g: 5～30mL, conjugated type;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and the solvent adding has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 10～70 ℃ of stirring and refluxing 10～72h, pour into after the cooling in the methyl alcohol, after the filtration; Solid formation vacuum-drying with obtaining obtains polyaniline derivative.
Wherein the solvent described in the step 1 is THF, N, N '-N,N-DIMETHYLACETAMIDE, N, a kind of or wherein several kinds the combination in N '-N, chloroform, N-Methyl pyrrolidone, toluene and the YLENE;
The structural formula that conjugated type in the step 1 gathers schiff bases is a positive integer for
n wherein, and Ar is
The application of above-mentioned polyaniline derivative is the application of polyaniline derivative as photovaltaic material.
Described photovaltaic material is that electrochromic material, fluorescent sensing material, acid cause sensing material, hole mobile material, third-order non-linear material, anti-fake material, camouflage material, automobile rearview mirror material or display material.
Polyaniline derivative is as the preparation method of electrochromism display material: polyaniline derivative is dissolved in the organic solvent, obtains polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass, obtain the electrochromism display material; Organic solvent wherein is THF, chloroform, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-N or N-Methyl pyrrolidone.
The application of above-mentioned polyaniline derivative is the application that polyaniline derivative detects as proton.
Polyaniline derivative as the application method that proton detects is: polyaniline derivative is dissolved in the organic solvent that contains proton; Obtain polyaniline derivative solution; Then polyaniline derivative solution is filmed on conductive glass; Obtain solid film, utilize the variation of solid film fluorescence intensity to detect proton concentration.
The reductive reaction formula that conjugation of the present invention is gathered schiff bases is:
Generate CH owing to gather the reduction of the two keys of C=NH in the schiff bases
2-NH key is that the solvability of the amine after the reduction improves, and contains CH
2The polyaniline derivative of-NH structure not only has electrochromic property, and has fluorescent detection capabilities.
The polyaniline derivative of the present invention's preparation is that the reduction that utilizes raw material to gather the two keys of C=NH in the schiff bases generates CH
2-NH key improves the solvability of the amine after the reduction, and contains CH
2The polyaniline derivative of-NH structure not only has electrochromic property, and has fluorescent detection capabilities.
The polyaniline derivative of the present invention's preparation is a monomer with three arylamine of propeller type; Can reduce the strong effect power between the polymer molecular chain effectively; Increase the solvability of polymkeric substance; While three arylamine are easy to form radical cation and demonstrate three arylamine that are different from neutral, and owing to contain two kinds of monomeric units in the structure, acting in conjunction makes polyaniline derivative 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 gathers schiff bases through reduction, makes its solvability that further increase arranged; And having former characteristic of gathering the adjustable transformation region of schiff bases simultaneously, this is that other materials is difficult to realize with this method.The polyaniline derivative that contains tri-arylamine group of the present invention 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 350 ℃.Have following meliority in the electrochromic property practical application of polyaniline derivative of the present invention: (1) has good electrochemical redox reversibility, through still keeping reversible after tens oxidation reduction cycle; (2) time of response of colour-change fast, after making alive, can rapid variable color within 0.4 second; (3) change in color is a reversible; (4) colour-change is highly sensitive; (5) higher cycle life is arranged; (6) the 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 after electrochromism in this experiment; (7) better chemical stability is arranged before and after the material variable color, under the normal temperature and pressure, maybe stable existence in the air.
Description of drawings
Fig. 1 tests the infrared spectrum of the polyaniline derivative of a preparation;
Fig. 2 tests the polyaniline derivative of a preparation
1The H nmr spectrum;
Fig. 3 tests the thermogravimetric curve figure of the polyaniline derivative of a preparation;
Fig. 4 tests the cyclic voltammogram of the polyaniline derivative of a preparation;
Fig. 5 tests the UV, visible light absorption curve figure of electrochromic process of the polyaniline derivative of a preparation; Wherein A is the UV, visible light absorption curve of current potential when being 0V; B is the UV, visible light absorption curve of current potential when being 0.8V; C is the UV, visible light absorption curve of current potential when being 1.0V; D is the UV, visible light absorption curve of current potential when being 1.1V, and E is the UV, visible light absorption curve of current potential when being 1.2V, and F is the UV, visible light absorption curve of current potential when being 1.3V;
Fig. 6 tests the fluorescence curve figure of the different trifluoroacetic acids of measuring of polyaniline derivative adding of a preparation; Wherein A is the fluorescence curve of the polyaniline derivative solution of 0 μ mol/L for trifluoroacetic acid concentration; B is the fluorescence curve of the polyaniline derivative solution of 3.72 μ mol/L for trifluoroacetic acid concentration; C is the fluorescence curve of the polyaniline derivative solution of 4.92 μ mol/L for trifluoroacetic acid concentration; D is the fluorescence curve of the polyaniline derivative solution of 6.12 μ mol/L for trifluoroacetic acid concentration, and E is the fluorescence curve of the polyaniline derivative solution of 7.32 μ mol/L for trifluoroacetic acid concentration;
Fig. 7 tests the infrared spectrum of the polyaniline derivative of two preparations;
Fig. 8 tests the polyaniline derivative of two preparations
1The H nmr spectrum;
Fig. 9 tests the thermogravimetric curve figure of the polyaniline derivative of two preparations;
Figure 10 tests the cyclic voltammogram of the polyaniline derivative of two preparations;
Figure 11 tests the UV, visible light absorption curve figure of electrochromic process of the polyaniline derivative of two preparations; Wherein A is the UV, visible light absorption curve of current potential when being 0V; B is the UV, visible light absorption curve of current potential when being 1.0V; C is the UV, visible light absorption curve of current potential when being 1.1V, and D is the UV, visible light absorption curve of current potential when being 1.2V, and E is the UV, visible light absorption curve of current potential when being 1.3V;
Figure 12 tests the fluorescence curve figure of the different trifluoroacetic acids of measuring of polyaniline derivative adding of two preparations; A is the fluorescence curve of the polyaniline derivative solution of 0 μ mol/L for trifluoroacetic acid concentration; B is the fluorescence curve of the polyaniline derivative solution of 3.6 μ mol/L for trifluoroacetic acid concentration; C is the fluorescence curve of the polyaniline derivative solution of 4.8 μ mol/L for trifluoroacetic acid concentration; D is the fluorescence curve of the polyaniline derivative solution of 7.2 μ mol/L for trifluoroacetic acid concentration; E is the fluorescence curve of the polyaniline derivative solution of 9.6 μ mol/L for trifluoroacetic acid concentration, and F is the fluorescence curve of the polyaniline derivative solution of 18 μ mol/L for trifluoroacetic acid concentration;
Figure 13 tests the infrared spectrum of the polyaniline derivative of three preparations;
Figure 14 tests the polyaniline derivative of three preparations
1The H nmr spectrum;
Figure 15 tests the thermogravimetric curve figure of the polyaniline derivative of three preparations;
Figure 16 tests the cyclic voltammogram of the polyaniline derivative of three preparations;
Figure 17 tests the infrared spectrum of the polyaniline derivative of four preparations
Figure 18 tests the polyaniline derivative of four preparations
1The H nmr spectrum;
Figure 19 tests the thermogravimetric curve figure of the polyaniline derivative of four preparations;
Figure 20 tests the cyclic voltammogram of the polyaniline derivative of four preparations;
Figure 21 tests the infrared spectrum of the polyaniline derivative of five preparations
Figure 22 tests the polyaniline derivative of five preparations
1The H nmr spectrum;
Figure 23 tests the thermogravimetric curve figure of the polyaniline derivative of five preparations;
Figure 24 tests the cyclic voltammogram of the polyaniline derivative of five preparations;
Embodiment
Embodiment one: the structural formula of the polyaniline derivative of this embodiment is following:
N is a positive integer in
formula, and Ar is
The polyaniline derivative of this embodiment is a monomer with three arylamine of propeller type; Can reduce the strong effect power between the polymer molecular chain effectively; Increase the solvability of polymkeric substance; While three arylamine are easy to form radical cation and demonstrate three arylamine that are different from neutral, and owing to contain two kinds of monomeric units in the structure, acting in conjunction makes polyaniline derivative 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 gathers schiff bases through reduction, makes its solvability that further increase arranged; And having former characteristic of gathering the adjustable transformation region of schiff bases simultaneously, this is that other materials is difficult to realize with this method.The polyaniline derivative that contains tri-arylamine group of the present invention 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 350 ℃.Have following meliority in the electrochromic property practical application of polyaniline derivative of the present invention: (1) has good electrochemical redox reversibility, through still keeping reversible after tens oxidation reduction cycle; (2) time of response of colour-change fast, after making alive, can rapid variable color within 0.4 second; (3) change in color is a reversible; (4) colour-change is highly sensitive; (5) higher cycle life is arranged; (6) the 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 after electrochromism in this experiment; (7) better chemical stability is arranged before and after the material variable color, under the normal temperature and pressure, maybe stable existence in the air.
Embodiment two: what this embodiment and embodiment one were different is that n is 3～10 positive integer.Other is identical with embodiment one.
Embodiment three: the preparation method that the reduction of the polyaniline derivative of this embodiment gathers schiff bases carries out according to the following steps:
One, the mass volume ratio that gathers schiff bases and solvent by conjugated type is that to gather in the schiff bases mole of C=N key and Peng Qinghuana be 1: 3～10 to take by weighing conjugated type and gather schiff bases, solvent and Peng Qinghuana for 1g: 5～30mL, conjugated type;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and the solvent adding has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 10～70 ℃ of stirring and refluxing 10～72h, pour into after the cooling in the methyl alcohol, after the filtration; Solid formation vacuum-drying with obtaining obtains polyaniline derivative.
The polyaniline derivative of this embodiment preparation is a monomer with three arylamine of propeller type; Can reduce the strong effect power between the polymer molecular chain effectively; Increase the solvability of polymkeric substance; While three arylamine are easy to form radical cation and demonstrate three arylamine that are different from neutral, and owing to contain two kinds of monomeric units in the structure, acting in conjunction makes polyaniline derivative 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 gathers schiff bases through reduction, makes its solvability that further increase arranged; And having former characteristic of gathering the adjustable transformation region of schiff bases simultaneously, this is that other materials is difficult to realize with this method.The polyaniline derivative that contains tri-arylamine group of the present invention 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 350 ℃.Have following meliority in the electrochromic property practical application of polyaniline derivative of the present invention: (1) has good electrochemical redox reversibility, through still keeping reversible after tens oxidation reduction cycle; (2) time of response of colour-change fast, after making alive, can rapid variable color within 0.4 second; (3) change in color is a reversible; (4) colour-change is highly sensitive; (5) higher cycle life is arranged; (6) the 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 after electrochromism in this experiment; (7) better chemical stability is arranged before and after the material variable color, under the normal temperature and pressure, maybe stable existence in the air.
Embodiment four: what this embodiment and embodiment three were different is that the solvent described in the step 1 is THF, N; N '-N,N-DIMETHYLACETAMIDE, N, a kind of or wherein several kinds the combination in N '-N, chloroform, N-Methyl pyrrolidone, toluene and the YLENE.Other is identical with embodiment three.
Embodiment five: this embodiment is different with embodiment three or four is that the structural formula that conjugated type in the step 1 gathers schiff bases is a positive integer for
n wherein, and Ar is that other is identical with embodiment three or four for
.
Embodiment six: this embodiment is different with one of embodiment three to five is that the temperature of the methyl alcohol in the step 2 is 0～25 ℃.Other is identical with one of embodiment three to five.
Embodiment seven: the application of embodiment one described polyaniline derivative is the application of polyaniline derivative as photovaltaic material.
Embodiment eight: this embodiment and embodiment seven are different is that described photovaltaic material is that electrochromic material, fluorescent sensing material, acid cause sensing material, hole mobile material, third-order non-linear material, anti-fake material, camouflage material, automobile rearview mirror material or display material.Other is identical with embodiment seven.
Embodiment nine: what this embodiment was different with embodiment seven or eight is: polyaniline derivative is dissolved in polyaniline derivative in the organic solvent as the preparation method of electrochromic material; Obtain polyaniline derivative solution; Then polyaniline derivative solution is filmed on conductive glass, obtain electrochromic material; Organic solvent wherein is THF, chloroform, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-N or N-Methyl pyrrolidone.
Embodiment ten: the application of embodiment one described polyaniline derivative is the application of polyaniline derivative as the proton test material.
Embodiment 11: polyaniline derivative as the application method that proton detects is: polyaniline derivative is dissolved in the organic solvent that contains proton; Obtain polyaniline derivative solution; Then polyaniline derivative solution is filmed on conductive glass; Obtain solid film, utilize the variation of solid film fluorescence intensity to detect proton concentration.
With following evidence beneficial effect of the present invention:
Test one: the preparation method that the reduction of the polyaniline derivative material of this test one gathers schiff bases carries out according to the following steps:
One, takes by weighing the 0.1777g conjugated type and gather schiff bases, 10mL THF and 0.0948g Peng Qinghuana;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and THF adding exsiccant has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 70 ℃ of stirring and refluxing 36h, pour temperature after the cooling into and be in 10 ℃ the methyl alcohol, then suction filtration; Be vacuum-drying 24h under 30 ℃ the condition with the solid formation that obtains, obtain polyaniline derivative in vacuum tightness 0.009MPa, temperature.
The structural formula that conjugated type described in the step 1 of this test gathers schiff bases is:
N wherein is 3～10.Its preparation method is: one, 0.3018g 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 drum; Divide after the mixed solution that then step 1 is obtained is divided into 3 parts and add dialdehyde-based compound and N in the reactor drum, N '-phenylbenzene-N 3 times; The mol ratio of N '-two (4-aniline) benzidine is 1: 1, then 160 ℃, the condition refluxed of nitrogen protection 10 hours, with the cold methanol polymkeric substance that settles out; Suction filtration, Suo Shi extracted 24 hours, oven dry; Promptly get and gather schiff bases, productive rate 86.76%; 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.
The structural formula of the polyaniline derivative that this test obtains is:
N wherein is 3～10.
The weight of the light yellow solid polyaniline derivative that this test obtains is 0.1651g, and productive rate is 93%.
The infrared spectrogram of the polyaniline derivative of this test one preparation is as shown in Figure 1, and Fig. 1 explains at wave number 3406cm
-1The place exists N-H stretching vibration characteristic peak, 1594cm
-1, 1511cm
-1, 1492cm
-1There is phenyl ring stretching vibration characteristic peak at the place.
The polyaniline derivative of this test one preparation
1H nuclear magnetic resonance nmr spectrogram is as shown in Figure 2, during test with CDCl
3Make solvent, there is the characteristic peak of hydrogen on the N-H in Fig. 2 explanation at chemical shift 4.26 places, and 7.49-6.60 is the peak of hydrogen on the phenyl ring.
Fig. 3 is the thermogravimetric curve figure of the polyaniline derivative of test one preparation; As can beappreciated from fig. 3, the polyaniline derivative of test one preparation is located weightlessness 5% when reaching 426 ℃, locates weightlessness 50% at 583 ℃, explains that the polyaniline derivative of this test one preparation has great high-temperature resistant.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 1mL; Obtain polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass, obtain electrochromic material; Be working electrode again with the electrochromic material; With the platinum filament is counter electrode, is reference electrode with the silver-silver chloride electrode, is that the acetonitrile solution that dewaters of 0.05～0.5mlo/L lithium perchlorate is as ionogen with concentration; Carry out the cyclic voltammetric test of polyaniline derivative, the cyclic voltammogram that obtains is as shown in Figure 4; As can be seen from Figure 4, the above peak of cyclic voltammetric 0V is an oxidation peak, contains 2 peaks, explains that this polymkeric substance has two kinds of oxidation state structures.Polyaniline derivative under impressed voltage, its electronic structure changes.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 1mL; Obtaining polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass, is working electrode with the conductive glass of filming again; With the platinum filament is counter electrode; With the silver-silver chloride electrode is reference electrode, and the acetonitrile solution that dewaters that with concentration is the 0.2mlo/L lithium perchlorate carries out the UV, visible light absorption curve of electrochromic process and measures as ionogen; The UV, visible light absorption curve of the electrochromic process of the polyaniline derivative that under different potentials, obtains is as shown in Figure 5; A is the UV, visible light absorption curve of current potential when being 0V, and B is the UV, visible light absorption curve of current potential when being 0.8V, and C is the UV, visible light absorption curve of current potential when being 1.0V; D is the UV, visible light absorption curve of current potential when being 1.1V; E is the UV, visible light absorption curve of current potential when being 1.2V, F be the UV, visible light absorption curve of current potential when being 1.3V as can beappreciated from fig. 5, the absorption peak of the polyaniline derivative of this test one preparation changes along with the variation of current potential.Peak at the 550nm place raises with the rising of current potential gradually, and the color of polymkeric substance changes and becomes red-violet colour by yellow, this polyaniline derivative generation metachromatism.That is to say that the color of different structure is different.
The polyaniline derivative of this test of 0.0036g preparation is dissolved in the THF of 100mL, and wherein the concentration of CN key is 10
-4Mol/L is diluted to 10
-5Mol/L obtains polyaniline derivative solution, adds different amount trifluoroacetic acids then respectively; Carry out the fluorescence curve test; The fluorescence curve figure that obtains is as shown in Figure 6, and wherein A is the fluorescence curve of the polyaniline derivative solution of 0 μ mol/L for trifluoroacetic acid concentration, and B is the fluorescence curve of the polyaniline derivative solution of 3.72 μ mol/L for trifluoroacetic acid concentration; C is the fluorescence curve of the polyaniline derivative solution of 4.92 μ mol/L for trifluoroacetic acid concentration; D is the fluorescence curve of the polyaniline derivative solution of 6.12 μ mol/L for trifluoroacetic acid concentration, and E is the fluorescence curve of the polyaniline derivative solution of 7.32 μ mol/L for trifluoroacetic acid concentration, as can beappreciated from fig. 6; Increase along with the trifluoroacetic acid amount; The fluorescence intensity of polyaniline derivative weakens, and visible novel polyphenyl sulfonamide derivatives is relatively more responsive to trifluoroacetic acid, can detect trifluoroacetic acid and other protonic acid reagent.
Test two: the preparation method that the reduction of the polyaniline derivative material of this test two gathers schiff bases carries out according to the following steps:
One, takes by weighing the 0.1577g conjugated type and gather schiff bases, 10mL THF and 0.0947g Peng Qinghuana;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and THF adding exsiccant has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 70 ℃ of stirring and refluxing 36h, pour temperature after the cooling into and be in 5 ℃ the methyl alcohol, then suction filtration; Be vacuum-drying 24h under 30 ℃ the condition with the solid formation that obtains, obtain polyaniline derivative in vacuum tightness 0.009MPa, temperature.
The structural formula that conjugated type described in the step 1 of this test gathers schiff bases is:
n wherein be 3～10 integer.Its preparation method is: one, 0.1756g dialdehyde-based triphenylamine is dissolved in the organic solvent, obtains mixed solution.Two, with 0.2553g 4,4 '-two amidos-4 " N-carbazyl triphenylamine 20ml organic solvent joins in the reactor drum, the mixed solution of step 1 preparation is divided to join in the reactor drum for 3 times again; dialdehyde-based compound and 4,4 in the reactor drum '-two amidos-4 " mol ratio of N-carbazyl triphenylamine is 1: 1, under temperature is 160 ℃, the condition of nitrogen protection, reacted 11 hours; Then with the cold methanol polymkeric substance that settles out; With methyl alcohol extracting polymer 36 hours, oven dry, promptly get and gather schiff bases again, productive rate is 64.0%; 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.
The structural formula of the polyaniline derivative that this test obtains is:
The weight of the pale solid polyaniline derivative that this test obtains is 0.1525g, and productive rate is 92%.
The infrared spectrogram of the polyaniline derivative of this test two preparations is as shown in Figure 7, as can beappreciated from fig. 7, and wave number 3400cm
-1The peak is the N-H vibration peak.1595cm
-1, 1505cm
-1Phenyl ring stretching vibration characteristic peak is arranged.
The polyaniline derivative of this test two preparations
1H nuclear magnetic resonance nmr spectrogram is as shown in Figure 8, during test with CDCl
3Make solvent, as can beappreciated from fig. 8, the chemical shift at 4.26 places is characteristic peaks of the H-N of polyaniline derivative.7.48-6.60 be the peak of hydrogen on the phenyl ring.
Fig. 9 is the thermogravimetric curve figure of the polyaniline derivative of test two preparations; As can beappreciated from fig. 9, the polyaniline derivative of test two preparations is located weightlessness 5% when reaching 411 ℃, locates weightlessness 50% at 577 ℃, explains that the polyaniline derivative of this test two preparations has great high-temperature resistant.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 0.5mL, obtains polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass ITO; Being working electrode with the conductive glass ITO that films again, is counter electrode with the platinum filament, is reference electrode with the silver-silver chloride electrode; The acetonitrile solution that dewaters that with concentration is the 0.1mlo/L lithium perchlorate carries out the cyclic voltammetric test of polyaniline derivative as ionogen, and the cyclic voltammogram that obtains is shown in figure 10; As can be seen from Figure 10, polyaniline derivative under impressed voltage, its electronic structure changes; That is to say that the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 2 peaks, explains that this polymkeric substance has two kinds of oxidation state structures.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 0.5mL, obtains polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass; Being working electrode with the conductive glass of filming again, is counter electrode with the platinum filament, is reference electrode with the silver-silver chloride electrode; The acetonitrile solution that dewaters that with concentration is the 0.2mlo/L lithium perchlorate is as ionogen; Carry out the UV, visible light absorption curve of electrochromic process and measure, the UV, visible light absorption curve of the electrochromic process of the polyaniline derivative that under different potentials, obtains is shown in figure 11, and A is the UV, visible light absorption curve of current potential when being 0V; B is the UV, visible light absorption curve of current potential when being 1.0V; C is the UV, visible light absorption curve of current potential when being 1.1V, and D is the UV, visible light absorption curve of current potential when being 1.2V, and E is the UV, visible light absorption curve of current potential when being 1.3V; As can beappreciated from fig. 11, the absorption peak of polyaniline derivative changes along with the variation of current potential.Peak at the 530nm place raises with the rising of current potential gradually, and the color of polymkeric substance changes, this polyaniline derivative generation metachromatism.
The polyaniline derivative of this test of 0.0031g preparation is dissolved in the THF of 100mL, and wherein the concentration of CN key is 10
-4Mol/L is diluted to 10
-5Mol/L obtains polyaniline derivative solution, adds different amount trifluoroacetic acids then respectively; Carry out the fluorescence curve test, the fluorescence curve figure that obtains is shown in figure 12, and wherein A is the fluorescence curve of the polyaniline derivative solution of 0 μ mol/L for trifluoroacetic acid concentration; B is the fluorescence curve of the polyaniline derivative solution of 3.6 μ mol/L for trifluoroacetic acid concentration; C is the fluorescence curve of the polyaniline derivative solution of 4.8 μ mol/L for trifluoroacetic acid concentration, and D is the fluorescence curve of the polyaniline derivative solution of 7.2 μ mol/L for trifluoroacetic acid concentration, and E is the fluorescence curve of the polyaniline derivative solution of 9.6 μ mol/L for trifluoroacetic acid concentration; F is the fluorescence curve of the polyaniline derivative solution of 18 μ mol/L for trifluoroacetic acid concentration; As can beappreciated from fig. 12, along with the increase of trifluoroacetic acid amount, the fluorescence intensity of polyaniline derivative weakens; It is thus clear that the novel polyphenyl sulfonamide derivatives is relatively more responsive to trifluoroacetic acid, can detect trifluoroacetic acid.
Test three: the preparation method that the reduction of the polyaniline derivative material of this test three gathers schiff bases carries out according to the following steps:
One, takes by weighing the 0.1588g conjugated type and gather schiff bases, 10mL THF and 0.0950g Peng Qinghuana;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and THF adding exsiccant has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 70 ℃ of stirring and refluxing 36h, pour temperature after the cooling into and be in 15 ℃ the methyl alcohol, then suction filtration; Be vacuum-drying 24h under 30 ℃ the condition with the solid formation that obtains, obtain polyaniline derivative in vacuum tightness 0.009MPa, temperature.
The structural formula that conjugated type described in the step 1 of this test gathers schiff bases is:
The structural formula of the polyaniline derivative that this test obtains is:
The weight of the light yellow solid polyaniline derivative that this test obtains is 0.1651g, and productive rate is 93%.
The infrared spectrogram of the polyaniline derivative of this test three preparations is shown in figure 13, as can beappreciated from fig. 13, and wave number 3400cm
-1The peak is the N-H vibration peak, 1589cm
-1, 1505cm
-1, 1491cm
-1Phenyl ring stretching vibration characteristic peak is arranged.
The polyaniline derivative of this test three preparations
1H nuclear magnetic resonance nmr spectrogram is shown in figure 14, during test with CDCl
3Make solvent, as can beappreciated from fig. 14, the chemical shift at 4.24 places is characteristic peaks of the H-N of polyaniline derivative, and 7.35～6.60 is the peak of hydrogen on the phenyl ring.
Figure 15 is the thermogravimetric curve figure of the polyaniline derivative of test three preparations; As can beappreciated from fig. 15, the polyaniline derivative of test three preparations is located weightlessness 5% when reaching 421 ℃, locates weightlessness 50% at 539 ℃, explains that the polyaniline derivative of this test three preparations has great high-temperature resistant.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 1mL, obtains polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass ITO; Being working electrode with the conductive glass ITO that films again, is counter electrode with the platinum filament, is reference electrode with the silver-silver chloride electrode; The acetonitrile solution that dewaters that with concentration is the 0.1mlo/L lithium perchlorate carries out the cyclic voltammetric test of polyaniline derivative as ionogen, and the cyclic voltammogram that obtains is shown in figure 16; As can beappreciated from fig. 16, polyaniline derivative under impressed voltage, its electronic structure changes; That is to say that the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 3 peaks, explains that this polymkeric substance has three kinds of oxidation state structures.
Test four: the preparation method that the reduction of the polyaniline derivative material of this test four gathers schiff bases carries out according to the following steps:
One, takes by weighing the 0.0585g conjugated type and gather schiff bases, 10mL THF and 0.0493g Peng Qinghuana;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and THF adding exsiccant has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 70 ℃ of stirring and refluxing 32h, pour temperature after the cooling into and be in 10 ℃ the methyl alcohol, then suction filtration; Be vacuum-drying 24h under 30 ℃ the condition with the solid formation that obtains, obtain polyaniline derivative in vacuum tightness 0.009MPa, temperature.
The structural formula that conjugated type described in the step 1 of this test gathers schiff bases is:
The structural formula of the polyaniline derivative that this test obtains is:
The weight of the light yellow solid polyaniline derivative that this test obtains is 0.0524g, and productive rate is 89%.
The infrared spectrogram of the polyaniline derivative of this test four preparations is shown in figure 17, as can beappreciated from fig. 17, and wave number 3400cm
-1The peak is the N-H vibration peak.1595.89cm
-1, 1505cm
-1, 1492cm
-1Phenyl ring stretching vibration characteristic peak is arranged.
The polyaniline derivative of this test four preparations
1H nuclear magnetic resonance nmr spectrogram is shown in figure 18, during test with CDCl
3Make solvent, as can beappreciated from fig. 18, the chemical shift at 4.26 places is characteristic peaks of the H-N of polyaniline derivative, and 7.27-6.57 is the peak of hydrogen on the phenyl ring.
Figure 19 is the thermogravimetric curve figure of the polyaniline derivative of test four preparations; As can beappreciated from fig. 19, the polyaniline derivative of test four preparations is located weightlessness 5% when reaching 353 ℃, locates weightlessness 50% at 729 ℃, explains that the polyaniline derivative of this test four preparations has great high-temperature resistant.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 0.8mL, obtains polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass ITO; Being working electrode with the conductive glass ITO that films again, is counter electrode with the platinum filament, is reference electrode with the silver-silver chloride electrode; The acetonitrile solution that dewaters that with concentration is the 0.1mlo/L lithium perchlorate carries out the cyclic voltammetric test of polyaniline derivative, shown in the cyclic voltammetric Figure 20 that obtains as ionogen; As can beappreciated from fig. 20, polyaniline derivative under impressed voltage, its electronic structure changes; That is to say that the color of different structure is different.The above peak of cyclic voltammetric 0V is an oxidation peak, contains 2 peaks, explains that this polymkeric substance has two kinds of oxidation state structures.
Test five: the preparation method that the reduction of the polyaniline derivative material of this test five gathers schiff bases carries out according to the following steps:
One, takes by weighing the 0.1844g conjugated type and gather schiff bases, 10mL THF and 0.09648g Peng Qinghuana;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and THF adding exsiccant has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 70 ℃ of stirring and refluxing 48h, pour temperature after the cooling into and be in 10 ℃ the methyl alcohol, then suction filtration; Be vacuum-drying 24h under 30 ℃ the condition with the solid formation that obtains, obtain polyaniline derivative in vacuum tightness 0.009MPa, temperature.
The structural formula that conjugated type described in the step 1 of this test gathers schiff bases is:
The structural formula of the polyaniline derivative that this test obtains is:
The weight of the light yellow solid polyaniline derivative that this test obtains is 0.1753g, and productive rate is 95%.
The infrared spectrogram of the polyaniline derivative of this test five preparations is shown in figure 21, can find out wave number 3406cm from Figure 21
-1The peak is the N-H vibration peak.1594cm
-1, 1500cm
-1Phenyl ring stretching vibration characteristic peak is arranged.
The polyaniline derivative of this test five preparations
1H nuclear magnetic resonance nmr spectrogram is shown in figure 22, during test with CDCl
3Make solvent, can find out from Figure 22, the chemical shift at 4.22 places is characteristic peaks of the H-N of polyaniline derivative, and 7.47-6.57 is the peak of hydrogen on the phenyl ring.
Figure 23 is the thermogravimetric curve figure of the polyaniline derivative of test five preparations; Can find out that from Figure 23 the polyaniline derivative of test five preparations is located weightlessness 7% when reaching 450 ℃, locates weightlessness 50% at 617 ℃, explain that the polyaniline derivative of this test four preparations has great high-temperature resistant.
The polyaniline derivative of this test of 0.1g preparation is dissolved in the THF of 0.9mL, obtains polyaniline derivative solution, then polyaniline derivative solution is filmed on conductive glass ITO; Being working electrode with the conductive glass ITO that films again, is counter electrode with the platinum filament, is reference electrode with the silver-silver chloride electrode; The acetonitrile solution that dewaters that with concentration is the 0.1mlo/L lithium perchlorate carries out the cyclic voltammetric test of polyaniline derivative, shown in the cyclic voltammetric Figure 24 that obtains as ionogen; Figure 24 explain polyaniline derivative that this 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, explains that this polymkeric substance has two kinds of oxidation state structures.
Claims (10)
1. polyaniline derivative is characterized in that the structural formula of polyaniline derivative is following:
N is a positive integer in
formula, and Ar is
2. polyaniline derivative according to claim 1 is characterized in that n in the structural formula of polyaniline derivative is 3～10 integer.
3. the reduction of polyaniline derivative as claimed in claim 1 gathers the preparation method of schiff bases, and the preparation method that the reduction that it is characterized in that polyaniline derivative gathers schiff bases carries out according to the following steps:
One, the mass volume ratio that gathers schiff bases and solvent by conjugated type is that to gather in the schiff bases mole of C=N key and Peng Qinghuana be 1: 3～10 to take by weighing conjugated type and gather schiff bases, solvent and Peng Qinghuana for 1g: 5～30mL, conjugated type;
Two, the conjugated type that earlier step 1 is taken by weighing gathers schiff bases and the solvent adding has in the there-necked flask of reflux; The Peng Qinghuana that again step 1 is taken by weighing joins in the there-necked flask; Be warming up to 10～70 ℃ of stirring and refluxing 10～72h, pour into after the cooling in the methyl alcohol, after the filtration; Solid formation vacuum-drying with obtaining obtains polyaniline derivative.
4. the reduction of polyaniline derivative according to claim 3 gathers the preparation method of schiff bases; It is characterized in that the solvent described in the step 1 is THF, N; N '-N,N-DIMETHYLACETAMIDE, N, a kind of or wherein several kinds the combination in N '-N, chloroform, N-Methyl pyrrolidone, toluene and the YLENE.
5. the reduction according to claim 3 or 4 described polyaniline derivatives gathers the preparation method of schiff bases, it is characterized in that the structural formula that conjugated type in the step 1 gathers schiff bases does
6. the reduction according to claim 3 or 4 described polyaniline derivatives gathers the preparation method of schiff bases, and the temperature that it is characterized in that the methyl alcohol in the step 2 is 0～25 ℃.
7. the application of polyaniline derivative as claimed in claim 1 is characterized in that the application of polyaniline derivative as photovaltaic material.
8. the application of polyaniline derivative according to claim 7 is characterized in that described photovaltaic material is that electrochromic material, fluorescent sensing material, acid cause sensing material, hole mobile material, third-order non-linear material, anti-fake material, camouflage material, automobile rearview mirror material or display material.
9. the application of polyaniline derivative according to claim 8; It is characterized in that polyaniline derivative as the preparation method of electrochromic material is: polyaniline derivative is dissolved in the organic solvent; Obtain polyaniline derivative solution; Then polyaniline derivative solution is filmed on conductive glass, obtain electrochromic material.Wherein organic solvent is THF, chloroform, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-N or N-Methyl pyrrolidone.
10. the application of polyaniline derivative as claimed in claim 1 is characterized in that the polyaniline derivative conduct is the application of polyaniline derivative verivate as the proton test material.
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| CN114805796A (en) * | 2022-03-08 | 2022-07-29 | 武汉大学 | Two-dimensional strong-fluorescence polyaniline material with metal ion detection performance and preparation method thereof |
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| CN101949072A (en) * | 2010-09-29 | 2011-01-19 | 黑龙江大学 | pH color-response sensing type micro-nanofiber, preparation method and application thereof |
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| CN113698306B (en) * | 2021-09-07 | 2022-07-22 | 吉林大学 | Diamine compound containing symmetric double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof |
| CN114805796A (en) * | 2022-03-08 | 2022-07-29 | 武汉大学 | Two-dimensional strong-fluorescence polyaniline material with metal ion detection performance and preparation method thereof |
| CN114805796B (en) * | 2022-03-08 | 2023-08-22 | 武汉大学 | Two-dimensional strong fluorescence polyaniline material with metal ion detection performance and preparation method thereof |
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