CN102634018A - Aminocarbazole/aniline copolymer and synthesis method thereof - Google Patents
Aminocarbazole/aniline copolymer and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses an aminocarbazole/aniline copolymer and a synthesis method thereof. The synthesis method comprises the following steps: dissolving 3-amino-9-ethylcarbazole and aniline in different mol ratios in a first solvent to form a comonomer solution; dissolving a certain amount of oxidant in a second solvent to form an oxidant solution; and after blending the oxidant solution and the comonomer solution, shaking intensely for some time, standing, and reacting completely to obtain the aminocarbazole/aniline copolymer. The invention has the advantages of simple synthesis steps, high efficiency and high controllability; and the obtained carbazole/aniline conducting polymer can be used in the fields of electrodes, electron screening, electrostatic prevention, electrochromic materials, fluoroscopic examination and the like.
Description
Technical field
The invention belongs to novel conjugatd polymers preparing technical field, be specifically related to a kind of aminocarbazole/benzene
Amine copolymer thing and compound method thereof.
Background technology
Conjugatd polymers had both had metal and semi-conductive electronic property as a kind of new-type functional material, had the easy processing of polymkeric substance, the mechanical equivalent of light feature of kindliness again.The quasi-one-dimensional macromolecular structure characteristic of conjugatd polymers is given its unique light, electricity, magnetic properties, thereby becomes the focus of applied research in recent years.
Polyaniline goes advantages such as doping effect with its inexpensive, simple and easy synthetic, high conductivity, the good and special acid doping/alkali of environmental stability, becomes by one of conjugatd polymers of broad research.(Tran H D; Li D; Kaner R B. One-dimensional conducting polymer nanostructures:Bulk synthesis and applications [J]. Advanced Materials; 2009,21 (14-15): 1487-1499.) polyaniline is showing huge application potential such as fields such as secondary cell, photodiode, electrochromic material and transmitters.Yet the solubility property of polyaniline itself is relatively poor, and it is very strong to be only soluble in polarity
N-methyl-pyrrolidone, and this solvent price is very expensive.In addition, the fluorescence property of polyaniline itself is also relatively poor.
Carbazole compound with its raw material be easy to get, heat-resisting, fluorescence property is strong, can form stable free positively charged ion (or hole) and high mobility characteristics, thereby is widely used in photoconduction, charge transport material.(Grazulevicius J V; Strohriegl P; Pielichowski J, Pielichowski K. Carbazole-containing polymers:Synthesis, properties and applications [J]. Progress in Polymer Science; 2003; 28 (9): 1297-1353.) it should be noted that 3-amino-9-ethyl carbazole (AEC) (structure is shown as shown in Figure 1) especially, give its excellent solubility property and modify characteristics such as property with easy chemistry owing to contain ethyl and amino.3-amino-9-ethyl carbazole and the dimeric similar of aniline can be through synthetic its corresponding polymer of chemical oxidative polymerization.Therefore, through 3-amino-9-ethyl carbazole and aniline are carried out copolyreaction, generate solubility property, resistance toheat that aminocarbazole/aniline will improve polyaniline, give polyaniline new fluorescence property, keep the characteristic of polyaniline high conductivity simultaneously.And synthesizing amino carbazole/aniline is expected to the advantage of comprehensive polycarbazole and polyaniline.
Summary of the invention
The objective of the invention is a kind ofly to gather carbazole and the polyaniline advantage is the novel conjugatd polymers material of one, promptly a kind of aminocarbazole/aniline in order to prepare.
Two of the object of the invention provides the compound method of above-mentioned a kind of aminocarbazole/aniline.
Technical scheme of the present invention
A kind of aminocarbazole/aniline, its general structural formula is as shown in Figure 2, and wherein polymerization degree n is 1～100.
The compound method of above-mentioned a kind of aminocarbazole/aniline specifically comprises the steps:
(1), 3-amino-9-ethyl carbazole (AEC) and aniline are dissolved in first kind of solvent and form comonomer solution;
Comonomer in the described comonomer solution promptly is made up of 3-amino-9-ethyl carbazole and aniline, and the molecular volume of described comonomer and first kind of solvent is than being 0.15mol/mL;
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the described comonomer: aniline is 0～90%:10～100%;
Described first kind of solvent is ethanol;
(2), oxygenant is dissolved in second kind of solvent and forms oxidizing agent solution;
The ratio of mixture of described oxygenant and second kind of solvent is calculated by the mole volume ratio, i.e. oxygenant: second kind of solvent is 1mmoL:2.5mL;
Described oxygenant is ammonium persulphate, iron trichloride or SRM 935a;
Described second kind of solvent is that concentration is hydrochloric acid, sulfuric acid, nitric acid or the perchloric acid solution of 1.0mol/L;
(3), calculate in molar ratio; Be comonomer: oxygenant is the ratio of 1:2, and the comonomer solution of step (1) gained is mixed the back controlled temperature with the oxidizing agent solution of step (2) gained be 25 ℃, and the time is that 24h carries out polyreaction; The synoptic diagram of its polymerization process is as shown in Figure 3; After polyreaction is intact reaction solution being taken out back control rotating speed is 12000r/min, and the time is 15min, and centrifugal settling obtains solid product;
The solid product of above-mentioned gained is used 8 times deionized water wash again, centrifugal settling, repetitive scrubbing-centrifugal three times finally obtains a kind of aminocarbazole/aniline 50 ℃ of following vacuum-dryings after 7 days.
Aminocarbazole/the aniline of gained of the present invention can be used for such as Application Areass such as electrode, screening of nucleus, anti-electrostatic, electrochromic material, fluoroscopic examinations.
Beneficial effect of the present invention
A kind of aminocarbazole/aniline of the present invention; Owing to be to utilize chemical oxidative polymerization method that 3-amino-9-ethyl carbazole and aniline are implemented copolymerization; A kind of aminocarbazole/aniline of synthetic, it is simple, efficient and highly controlled therefore to have compound method, and productive rate can be up to 68%.
A kind of aminocarbazole/aniline of the present invention has excellent conductive performance, and its electric conductivity can be kept 0.1～1S/cm order of magnitude; And have the good photic look that turns blue, green-emitting fluorescence property and have good thermal stability.
In addition, a kind of aminocarbazole/aniline of the present invention owing to have good dissolving or solvent dispersion property, therefore can solve the unmanageable technical barrier of conductive polymers.
In sum, a kind of aminocarbazole/aniline of the present invention combines the advantage of polycarbazole and two kinds of conductive polymerss of polyaniline, and its productive rate, conductivity, fluorescence property height are controlled, have realized the conjugatd polymers multifunction.
Description of drawings
The structural representation of Fig. 1,3-amino-9-ethyl carbazole (AEC);
The structural formula synoptic diagram of Fig. 2, a kind of aminocarbazole/aniline of the present invention, wherein n is 1～100;
The preparing method's of Fig. 3, aminocarbazole/aniline of the present invention polymerization process synoptic diagram;
AEC content is respectively 10%, 30%, 50%, 70% and the uv absorption spectra of 90% o'clock resulting aminocarbazole/aniline among Fig. 4, the embodiment 2～6;
AEC content is 0%, 10%, 30%, 50%, 70% and the infrared absorpting light spectra of 90% o'clock resulting aminocarbazole/aniline among Fig. 5, the embodiment 1～6;
AEC content is 0%, 10%, 30%, 50% and the thermal analysis curve of 70% o'clock resulting aminocarbazole/aniline among Fig. 6, the embodiment 1～5;
AEC content is 0%, 10%, 30%, 50% and volt-ampere (I-V) curve of 70% o'clock resulting aminocarbazole/aniline among Fig. 7, the embodiment 1～5;
The scanning electron microscope diagram sheet of the polyaniline of Fig. 8 a, embodiment 1 gained;
AEC content is the scanning electron microscope diagram sheet of the aminocarbazole/aniline of 10% o'clock gained among Fig. 8 b, the embodiment 2;
AEC content is the scanning electron microscope diagram sheet of the aminocarbazole/aniline of 30% o'clock gained among Fig. 8 c, the embodiment 3;
AEC content is the scanning electron microscope diagram sheet of the aminocarbazole/aniline of 50% o'clock gained among Fig. 8 d, the embodiment 4;
AEC content is the scanning electron microscope diagram sheet of the aminocarbazole/aniline of 70% o'clock gained among Fig. 8 e, the embodiment 5;
AEC content is the scanning electron microscope diagram sheet of the aminocarbazole/aniline of 90% o'clock gained among Fig. 8 f, the embodiment 6;
AEC content is the transmission electron micrograph of the aminocarbazole/aniline of 50% o'clock gained among Fig. 9 a, the embodiment 4;
AEC content is the transmission electron micrograph of the aminocarbazole/aniline of 70% o'clock gained among Fig. 9 b, the embodiment 5;
AEC content is the transmission electron micrograph of the aminocarbazole/aniline of 90% o'clock gained among Fig. 9 c, the embodiment 6.
Embodiment
Below through embodiment and combine accompanying drawing that the present invention is further set forth, but do not limit the present invention.
The apparent calculation of yield of a kind of aminocarbazole/aniline of gained of the present invention is passed through following formula (1):
Wherein, M
1Be 3-amino-monomeric charging capacity of 9-ethyl carbazole (g);
M
2Charging capacity (g) for aniline monomer;
M
0Quality (g) for the aminocarbazole/aniline of final gained.
The structure, form and the performance characterization method that the present invention relates to multipolymer are following:
Uv absorption spectrum characterizes
Adopt Lambda 750 type UVSs, at room temperature aminocarbazole/aniline nanometer aqueous dispersions of about 0.001～0.005 g/L of concentration is tested.
Infrared absorption spectrum characterizes
Adopt Spectrum100 type FTIR Spectrometer FTIR, at room temperature aminocarbazole/aniline powder is tested.
Sem characterizes
Aminocarbazole/aniline nanometer aqueous dispersions is directly dropped on the silicon chip, treat the sample seasoning after, adopt Quanta FEG 430 type field emission scanning electron microscopes that its microscopic appearance is observed; Before observing sample all being carried out metal spraying (Pt) handles.
Transmission electron microscope characterizes
Aminocarbazole/aniline nanometer aqueous dispersions is directly dropped on the copper mesh of Formvar or carbon spraying, treat the sample seasoning after, adopt FEI TF30 type transmission electron microscope that its microscopic appearance is observed.
The thermal stability test
Adopt Pyris 1 TGA calorimetric analysis appearance, under the room temperature nitrogen atmosphere aminocarbazole/aniline powder is tested 10 ℃/min of temperature rise rate under room temperature～1100 ℃.
The solubility property test
5mg aminocarbazole/aniline powder is scattered in the 1mL organic solvent, and ultra-sonic dispersion 10min at room temperature, remaining through color and the particulate of observing dispersion liquid, sxemiquantitative characterizes the solubility property of aminocarbazole/aniline.
The fluorescence property test
Aminocarbazole/aniline ethanolic soln is positioned under the uv lamp of 365nm wavelength irradiation and judges fluorescence property and intensity qualitatively.
Conductivity test
Take by weighing the dry good aminocarbazole/aniline powder of 80mg, utilize infrared tabletting machine that it is pressed into the sequin of certain thickness (d); Evenly coat two parallel elargol lines that length and spacing are 1cm in the identical faces of compressing tablet then; After treating the elargol drying, utilize volt-ampere (I-V) curve of Keithley2400 type probe station test aminocarbazole/aniline, draw its square resistance (
R Sq ); According to formula (2) electric conductivity of aminocarbazole/aniline is calculated.
Wherein, parallel the carrying out 5 times of all specific conductivity tests averaged then.
The instrument that the present invention is used
The uv absorption spectrum appearance, Lambda 750 types, U.S. PE company.
Infrared absorption spectrometer, Spectrum100 type, U.S. PE company.
Field emission scanning electron microscope, Quanta FEG 430 types, Dutch PHILIPS Co..
Transmission electron microscope, FEI TF30 type, Dutch PHILIPS Co..
Two probe conduction rate testers, Keithley2400 type, U.S. Keithley instrument company.
Thermal analyzer, Pyris 1 TGA type, U.S. PE company.
3-amino-9-ethyl carbazole and aniline are available from German Sigma-Aldrich company; Ethanol, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, ammonium persulphate, iron trichloride and SRM 935a etc. are all available from Shanghai traditional Chinese medicines reagent ltd.
Embodiment 1
Pure polyaniline is the synthetic of aminocarbazole/aniline (0/100) multipolymer
Aminocarbazole/aniline copolymerization mol ratio is 0/100, promptly accurately takes by weighing 186mg (2mmol) aniline and is dissolved in 13mL ethanol, forms monomer solution;
According to oxygenant and aniline monomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Pour oxidizing agent solution into aniline monomer solution, acutely rock 10 seconds after, controlled temperature is 25 ℃, standing and reacting 24h.After question response finishes, reaction solution is taken out back centrifugal settling obtain solid product, use the deionized water wash product; Use 8 times deionized water wash solid product again, centrifugal settling, repetitive scrubbing-centrifugal three times, flush away oligopolymer, byproduct of reaction, oxygenant and small molecules acid etc. finally obtain pure polyaniline sample.
Leave and take the aqueous dispersions of minute quantity, be used as the sample of uv absorption spectrum, sem and transmission electron microscope test; Remaining sample after 7 days, obtains the black polyaniline powder 50 ℃ of following vacuum-dryings, weighs.
Synthesizing of aminocarbazole/aniline (10/90) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 10/90, promptly accurately takes by weighing 42mg (0.2mmol) aminocarbazole and 168mg (1.8mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Pour oxidizing agent solution into aminocarbazole/aniline comonomer solution, acutely rock 10 seconds after, controlled temperature is 25 ℃, standing and reacting 24h.After question response finishes, reaction solution is taken out back centrifugal settling obtain solid product, use the deionized water wash product; Use 8 times deionized water wash solid product again, centrifugal settling, repetitive scrubbing-centrifugal three times, flush away oligopolymer, byproduct of reaction, oxygenant and small molecules acid etc. finally obtain aminocarbazole/aniline (10/90) copolymer sample.
Leave and take the aqueous dispersions of minute quantity, be used as the sample of uv absorption spectrum, sem and transmission electron microscope test; Remaining sample after 7 days, obtains black aminocarbazole/aniline (10/90) copolymer powder 50 ℃ of following vacuum-dryings, weighs.
Embodiment 3
Synthesizing of aminocarbazole/aniline (30/70) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 30/70, promptly accurately takes by weighing 126mg (0.6mmol) aminocarbazole and 130mg (1.4mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Pour oxidizing agent solution into aminocarbazole/aniline comonomer solution, acutely rock 10 seconds after, controlled temperature is 25 ℃, standing and reacting 24h.After question response finishes, reaction solution is taken out back centrifugal settling obtain solid product, use the deionized water wash product; Use 8 times deionized water wash solid product again, centrifugal settling, repetitive scrubbing-centrifugal three times, flush away oligopolymer, byproduct of reaction, oxygenant and small molecules acid etc. finally obtain aminocarbazole/aniline (30/70) copolymer sample.
Leave and take the aqueous dispersions of minute quantity, be used as the sample of uv absorption spectrum, sem and transmission electron microscope test; Remaining sample after 7 days, obtains black aminocarbazole/aniline (30/70) copolymer powder 50 ℃ of following vacuum-dryings, weighs.
Synthesizing of aminocarbazole/aniline (50/50) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 50/50, promptly accurately takes by weighing 210mg (1mmol) aminocarbazole and 93mg (1mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Pour oxidizing agent solution into aminocarbazole/aniline comonomer solution, acutely rock 10 seconds after, controlled temperature is 25 ℃, standing and reacting 24h.After question response finishes, reaction solution is taken out back centrifugal settling obtain solid product, use the deionized water wash product; Use 8 times deionized water wash solid product again, centrifugal settling, repetitive scrubbing-centrifugal three times, flush away oligopolymer, byproduct of reaction, oxygenant and small molecules acid etc. finally obtain aminocarbazole/aniline (50/50) copolymer sample.
Leave and take the aqueous dispersions of minute quantity, be used as the sample of uv absorption spectrum, sem and transmission electron microscope test; Remaining sample after 7 days, obtains black aminocarbazole/aniline (50/50) copolymer powder 50 ℃ of following vacuum-dryings, weighs.
Embodiment 5
Synthesizing of aminocarbazole/aniline (70/30) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 70/30, promptly accurately takes by weighing 294mg (1.4mmol) aminocarbazole and 56mg (0.6mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Pour oxidizing agent solution into aminocarbazole/aniline comonomer solution, acutely rock 10 seconds after, controlled temperature is 25 ℃, after standing and reacting 24h, question response finish, reaction solution is taken out back centrifugal settling obtain solid product, uses the deionized water wash product; Use 8 times deionized water wash solid product again, centrifugal settling, repetitive scrubbing-centrifugal three times, flush away oligopolymer, byproduct of reaction, oxygenant and small molecules acid etc. finally obtain aminocarbazole/aniline (70/30) copolymer sample.
Leave and take the aqueous dispersions of minute quantity, be used as the sample of uv absorption spectrum, sem and transmission electron microscope test; Remaining sample after 7 days, obtains black aminocarbazole/aniline (70/30) copolymer powder 50 ℃ of following vacuum-dryings, weighs.
Synthesizing of aminocarbazole/aniline (90/10) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 90/10, promptly accurately takes by weighing 378mg (1.8mmol) aminocarbazole and 19mg (0.2mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Pour oxidizing agent solution into aminocarbazole/aniline comonomer solution, acutely rock 10 seconds after, controlled temperature is 25 ℃, standing and reacting 24h.After question response finishes, reaction solution is taken out back centrifugal settling obtain solid product, use the deionized water wash product; Use 8 times deionized water wash solid product again, centrifugal settling, repetitive scrubbing-centrifugal three times, flush away oligopolymer, byproduct of reaction, oxygenant and small molecules acid etc. finally obtain aminocarbazole/aniline (90/10) copolymer sample.
Leave and take the aqueous dispersions of minute quantity, be used as the sample of uv absorption spectrum, sem and transmission electron microscope test; Remaining sample after 7 days, obtains black aminocarbazole/aniline (90/10) copolymer powder 50 ℃ of following vacuum-dryings, weighs.
Calculate according to formula (1); The polyaniline of the above embodiments 1-6 gained and aminocarbazole/aniline; Promptly when AEC content was 0%, 10%, 30%, 50%, 70% and 90%, its productive rate was respectively 77.7%, 67.9%, 68.8%, 67.9%, 48.8% and 4.9%.Increased to 50% o'clock from 10% with AEC content, the productive rate of aminocarbazole/aniline is constant basically, maintains 68% level, compares pure polyaniline productive rate and descends slightly.Increased to 70% o'clock from 50% with AEC content, aminocarbazole/aniline productive rate drops to 48.8%.When continuing to increase AEC content to 90%, aminocarbazole/aniline productive rate is merely 4.9%.The reason that such trend occurs is: AEC and aniline reaction generate in the process of aminocarbazole/aniline; The amount of participating in the aniline that reacts is more; It is many more to generate the contained aniline chain link of aminocarbazole/aniline, and its solubility property is relatively poor relatively, and the amount that in the product sepn process, keeps is high more.And along with the continuous increase of AEC content, it is many more to generate the contained AEC chain link of aminocarbazole/aniline.Because AEC can be soluble in ethanol, in the product sepn process, there is part aminocarbazole/aniline to be fallen as separation of by-products.
The uv absorption spectra of the polyaniline of the above embodiments 2-6 gained and aminocarbazole/aniline (being that AEC content is respectively 10%, 30%, 50%, 70% and 90%) is seen shown in Figure 4.
As can beappreciated from fig. 4; When AEC content is 10%; Aminocarbazole/aniline has the typical big π structure of conjugated polymers macromole, the typical conjugation absorption peak of conjugated polymers macromole occurs at 520nm, 650nm and 805nm place, and the characteristic ultraviolet absorption of this and polyaniline is closely similar.(Huang J X; Kaner R B. A general chemical route to polyaniline nanofibers [J]. Journal of the American Chemistry Society; 2004; 126 (3): 851-855) when AEC content is 30%, multipolymer has kept the ultraviolet absorption peak of 520nm, 605nm wavelength, and at the strength reduction of the absorption peak of 805nm wavelength.When increasing to 50-90% along with AEC content, aminocarbazole/aniline only ultraviolet absorption peak occurs at the 520nm place.This shows that < 50% the time, aminocarbazole/>aniline presents the typical characteristic ultraviolet absorption of polyaniline when AEC content; Otherwise aminocarbazole/aniline presents the typical characteristic ultraviolet absorption that gathers aminocarbazole.
The infrared absorpting light spectra of the polyaniline of the above embodiments 1-6 gained and aminocarbazole/aniline (being that AEC content is respectively 10%, 30%, 50%, 70% and 90%) is as shown in Figure 5.
As can beappreciated from fig. 5, pure polyaniline is at 1587cm
-1, 1497cm
-1, 1307cm
-1With 1153 cm
-1The place presents quinoid structure, benzene formula structure, C N structure and N quinoid N typical infrared absorption peaks such as (electronics shape absorption bands).(Liao Y Z, Zhang C, Zhang Y; Strong V, Tang J S, Li X-G; Kalantar-zadeh K, Hoek E M V, Wang K L; Kaner R B. Carbon nanotube/ polyaniline composite nanofibers:Facile synthesis and chemosensors [J]. Nano Letters; 2011,11 (3): after 954-959.) copolymerization takes place in aniline and 10%, 30%, 50%, 70% and 90% AEC, the corresponding infrared absorption peak of aminocarbazole/aniline benzene formula structure respectively red shift to 1496cm
-1, 1490cm
-1, 1487cm
-1, 1485cm
-1And 1476cm
-1And when AEC content was 70% and 90%, the ir absorption of the benzene formula structure of aminocarbazole/aniline split into two peaks, lays respectively at 1485cm
-1/ 1475cm
-1And 1476cm
-1/ 1463cm
-1In addition, the corresponding infrared absorption peak of aminocarbazole/aniline C N structure is blue shifted to 1303cm respectively
-1, 1313cm
-1, 1314cm
-1, 1315cm
-1And 1316cm
-1
Can know with ultra-violet analysis from infrared; Prepared aminocarbazole/aniline has the big π constitutional features of the macromolecular typical case of conjugated polymers; And find that its structure is nonlinearities change with monomer mole ratio, confirmed that prepared product is aniline and 3-amino-9-ethyl carbazole multipolymer really.
The thermogravimetric curve of the polyaniline of the above embodiments 1-5 gained and aminocarbazole/aniline (being that AEC content is respectively 10%, 30%, 50% and 70%) is seen Fig. 6.
As can beappreciated from fig. 6, prepared product has the good thermal stability of conjugated polymers macromole, and the thermal weight loss phenomenon does not take place polymkeric substance basically before 200 ℃.Along with the rising of temperature, violent thermal weight loss takes place in polyaniline, and the carbon yield of polymkeric substance is merely 15% in the time of 1000 ℃; And after copolymerization took place aniline and 10%, 30% and 50% AEC, the weightless degree of polymkeric substance reduced greatly, 1000
oCarbon yield during C is increased to 42.2%, 50.1% and 53.3% respectively.This is the introducing because of the carbazole chain link, because its high condensed ring aromaticity and high-carbon content, the resistance toheat that causes generating aminocarbazole/aniline is improved greatly.It should be noted that when AEC content increases to 70% the carbon yield of aminocarbazole/aniline in the time of 1000 ℃ drops to 47.1% slightly.This possibly be because, the introducing of a large amount of AEC chain links, the contained ethyl side groups content of the aminocarbazole/aniline of generation is very high.And the thermostability of ethyl side groups is relatively poor, when thermal treatment, produces weightlessness easily, finally causes the carbon yield of aminocarbazole/aniline slightly to descend.Thermogravimetic analysis (TGA) shows further that also aniline and 3-amino-9-ethyl carbazole reaction has generated both multipolymers really.
The polyaniline of the above embodiments 1-6 gained and aminocarbazole/aniline (being that AEC content is respectively 10%, 30%, 50%, the 70% and 90%) solubility property in organic solvent is seen table 1.
Can find out that from table 1 solubility property of pure polyaniline in most solvents is relatively poor, and aminocarbazole/aniline can be dissolved in most of organic solvent, explains that the introducing of AEC chain link has improved the solubility property of polyaniline.
The dissolving situation of pure polyaniline of table 1 and AEC multipolymer thereof (: insoluble; +: dissolving)
The polyaniline and the aminocarbazole/aniline (being that AEC content is respectively 0%, 10%, 30%, 50%, 70% and 90%) of embodiment 1-6 gained are dispersed or dissolved in ethanol formation 0.05g/mL solution.Under 356nm wavelength ultra violet lamp, polyaniline does not produce fluorescence phenomenon; And obvious pl-phenomenon has taken place in aminocarbazole/aniline.Increase to 30%, 50%, 70% and with AEC content respectively at 90% o'clock from 10%, that multipolymer appears is sky blue, sea blue, pale green, green and deep green fluorescence.This explanation, copolymerization process not only gives polyaniline new fluorescence property, can regulate and control its fluorescence color through the regulation and control copolymerization ratio.
The polyaniline of embodiment 1-5 gained and the I-V curve of aminocarbazole/aniline (being that AEC content is respectively 10%, 30%, 50% and 70%) pressed powder are seen Fig. 7.
Can calculate through Fig. 7, AEC content is 0%, 10%, 30%, 50% and 70% o'clock, and the square resistance of polymkeric substance is respectively 224.8 Ω/mm
2, 372.1 Ω/mm
2, 598.3 Ω/mm
2, 1640.8 Ω/mm
2And 4.1 * 10
6Ω/mm
2According to formula (2) and compressing tablet thickness thereof, the electric conductivity of emergencing copolymer is respectively 1.2S/cm, 0.52S/cm, 0.33S/cm, 0.11S/cm and 4.9 * 10
-4S/cm.Along with AEC content raises, the electric conductivity of aminocarbazole/aniline is non-linear downtrending.When AEC content≤50%, the electric conductivity of aminocarbazole/aniline is kept and the same order of magnitude scope of the electric conductivity of pure polyaniline, shows that its conductivity is better.And when AEC content increases to 70%; The electric conductivity of aminocarbazole/aniline seriously descends; This possibly be because too much introduced ethyl side groups; Make the same planar alignment of the difficult coexistence of carbazole and aniline ring, finally cause the conjugate planes of aminocarbazole/aniline macromolecular chain to be damaged, be unfavorable for transporting of electronics or current carrier.Therefore, in order to keep the polyaniline excellent electric conductivity, and give its unique fluorescence property, the copolymerization ratio of aniline and 3-amino-9-ethyl carbazole be 50/50 o'clock comparatively suitable.
The polyaniline of embodiment 1-6 gained and the scanning electron microscope diagram sheet of aminocarbazole/aniline (being that AEC content is respectively 10%, 30%, 50%, 70% and 90%) are seen Fig. 8 a, Fig. 8 b, Fig. 8 c, Fig. 8 d, Fig. 8 e and Fig. 8 f respectively.
Can find out that from 8a, Fig. 8 b, Fig. 8 c, Fig. 8 d, Fig. 8 e and Fig. 8 f pure polyaniline and AEC content are that aminocarbazole/aniline of 10% all presents unformed microscopic pattern; And when AEC content is 30-90%, aminocarbazole/aniline appear have regular shape, mean diameter be 2-5 μ m the micron ball.Simultaneously, transmission electron microscope observation is found (Fig. 9 a, Fig. 9 b and Fig. 9 c), and these microns ball has a kind of hollow structure of uniqueness.
Embodiment 7
With the iron trichloride is oxygenant, synthesizing amino carbazole/aniline (50/50) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 50/50, promptly accurately takes by weighing 210mg (1mmol) aminocarbazole and 93mg (1mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant iron trichloride 648mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Embodiment 8
With the SRM 935a is oxygenant, synthesizing amino carbazole/aniline (50/50) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 50/50, promptly accurately takes by weighing 210mg (1mmol) aminocarbazole and 93mg (1mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant SRM 935a 1176mg (4mmol) and be dissolved in 10mL 1.0mol/L hydrochloric acid soln, forms oxidizing agent solution.
Embodiment 9
With 1.0mol/L nitric acid is medium, synthesizing amino carbazole/aniline (50/50) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 50/50, promptly accurately takes by weighing 210mg (1mmol) aminocarbazole and 93mg (1mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L salpeter solution, forms oxidizing agent solution.
With 1.0mol/L sulfuric acid is medium, synthesizing amino carbazole/aniline (50/50) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 50/50, promptly accurately takes by weighing 210mg (1mmol) aminocarbazole and 93mg (1mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L sulphuric acid soln, forms oxidizing agent solution.
Embodiment 11
With 1.0mol/L perchloric acid is medium, synthesizing amino carbazole/aniline (50/50) multipolymer
The mol ratio of aminocarbazole/aniline copolymerization is 50/50, promptly accurately takes by weighing 210mg (1mmol) aminocarbazole and 93mg (1mmol) aniline is dissolved in 13mL ethanol, forms comonomer solution;
According to oxygenant and comonomer mol ratio is 2/1 to take by weighing oxygenant ammonium persulphate 912mg (4mmol) and be dissolved in 10mL 1.0mol/L perchloric acid solution, forms oxidizing agent solution.
Above-mentioned specific embodiment just is used for the present invention that explains, rather than limits the invention, and in spirit of the present invention and claim protection domain, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (8)
1. aminocarbazole/aniline is characterized in that its structural formula is as follows:
Wherein polymerization degree n is 1～100.
2. the compound method of a kind of aminocarbazole/aniline as claimed in claim 1 is characterized in that bag
Draw together following steps:
(1), 3-amino-9-ethyl carbazole and aniline are dissolved in first kind of solvent formation comonomer solution;
Comonomer in the described comonomer solution promptly is made up of 3-amino-9-ethyl carbazole and aniline, and the molecular volume of described comonomer and first kind of solvent is than being 0.15mol/mL;
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the described comonomer: aniline is 0～90%:10～100%;
Described first kind of solvent is ethanol;
(2), oxygenant is dissolved in second kind of solvent and forms oxidizing agent solution;
The ratio of mixture of described oxygenant and second kind of solvent is calculated by the mole volume ratio, i.e. oxygenant: second kind of solvent is 1mmoL:2.5mL;
Described oxygenant is ammonium persulphate, iron trichloride or SRM 935a;
Described second kind of solvent is that concentration is hydrochloric acid, sulfuric acid, nitric acid or the perchloric acid solution of 1.0mol/L;
(3), calculate in molar ratio; Be comonomer: oxygenant is the ratio of 1:2; The comonomer solution of step (1) gained is mixed the back controlled temperature with the oxidizing agent solution of step (2) gained be 25 ℃, and the time is that 24h carries out polyreaction, and after polyreaction is intact reaction solution being taken out back control rotating speed is 12000r/min; Time is 15min, and centrifugal settling obtains solid product;
The solid product of above-mentioned gained is used 8 times deionized water wash again, centrifugal settling, repetitive scrubbing-centrifugal three times finally obtains a kind of aminocarbazole/aniline 50 ℃ of following vacuum-dryings after 7 days.
3. the compound method of a kind of aminocarbazole/aniline as claimed in claim 2 is characterized in that,
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the comonomer described in the step (1): aniline is 0%:100%.
4. the compound method of a kind of aminocarbazole/aniline as claimed in claim 2 is characterized in that,
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the comonomer described in the step (1): aniline is 10%:90%.
5. the compound method of a kind of aminocarbazole/aniline as claimed in claim 2 is characterized in that,
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the comonomer described in the step (1): aniline is 30%:70%.
6. the compound method of a kind of aminocarbazole/aniline as claimed in claim 2 is characterized in that,
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the comonomer described in the step (1): aniline is 50%:50%.
7. the compound method of a kind of aminocarbazole/aniline as claimed in claim 2 is characterized in that,
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the comonomer described in the step (1): aniline is 70%:30%.
8. the compound method of a kind of aminocarbazole/aniline as claimed in claim 2 is characterized in that,
3-amino-9-ethyl carbazole and aniline are pressed mole percentage calculation, i.e. a 3-amino-9-ethyl carbazole in the comonomer described in the step (1): aniline is 90%:10%.
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| JP2017002287A (en) * | 2015-06-05 | 2017-01-05 | 三菱化学株式会社 | Polymer, composition for organic electroluminescent element, organic electroluminescent element, organic el display device and electronic el lighting |
| CN113278148A (en) * | 2021-04-28 | 2021-08-20 | 厦门大学 | Bipyridine/aniline copolymer loaded copper ion molecule and preparation method thereof |
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| JP2010059224A (en) * | 2008-09-01 | 2010-03-18 | Dainichiseika Color & Chem Mfg Co Ltd | Pigment dispersant, color composition for color filter and color filter |
| WO2011146379A1 (en) * | 2010-05-20 | 2011-11-24 | Lubrizol Advanced Materials, Inc. | Dispersant composition |
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| JP2010059224A (en) * | 2008-09-01 | 2010-03-18 | Dainichiseika Color & Chem Mfg Co Ltd | Pigment dispersant, color composition for color filter and color filter |
| WO2011146379A1 (en) * | 2010-05-20 | 2011-11-24 | Lubrizol Advanced Materials, Inc. | Dispersant composition |
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| JP2017002287A (en) * | 2015-06-05 | 2017-01-05 | 三菱化学株式会社 | Polymer, composition for organic electroluminescent element, organic electroluminescent element, organic el display device and electronic el lighting |
| CN113278148A (en) * | 2021-04-28 | 2021-08-20 | 厦门大学 | Bipyridine/aniline copolymer loaded copper ion molecule and preparation method thereof |
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