CN105085501A - Triphenylamine bithienylpyrrole compound containing methyl and preparation method , and polymer prepared from the compound and preparation method and application thereof - Google Patents

Triphenylamine bithienylpyrrole compound containing methyl and preparation method , and polymer prepared from the compound and preparation method and application thereof Download PDF

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CN105085501A
CN105085501A CN201510566723.2A CN201510566723A CN105085501A CN 105085501 A CN105085501 A CN 105085501A CN 201510566723 A CN201510566723 A CN 201510566723A CN 105085501 A CN105085501 A CN 105085501A
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thienopyrroles
methylic
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triphenylamine base
volume ratio
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CN105085501B (en
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牛海军
蔡姝崴
蒲丽莉
郑冰
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Heilongjiang University
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract

The invention provides a triphenylamine bithienylpyrrole compound containing methyl and a preparation method, and a polymer prepared from the compound and a preparation method and application thereof, and relates to a pyrrole compound and a preparation method thereof, and a polymer prepared from the compound and a preparation method and application thereof. The purpose of the present invention is to solve the problems of poor film formation and single color changing of the electrochromic polymer in the prior art. The structural formula of the compound is as described. The preparation method of the compound comprises: adding 2,5-di(2-thienyl)-1,4-butanedione monomer, N'-(4-aminophenyl)-N'- p-methyl-phenyl-1,4-diamine and p-toluenesulfonic acid into toluene, then conducting heating reflux and rotary evaporation to obtain the compound. The structural formula of the polymer is as below. The polymer is prepared by polymerizing the compound. The triphenylamine bithienylpyrrole compound containing methyl can be used as a multifunctional organic polymer in electrochromic material, optoelectronic device and biosensor. The invention can obtain the triphenylamine bithienylpyrrole compound containing methyl.

Description

The two Thienopyrroles compound of methylic triphenylamine base and preparation method and the polymkeric substance utilizing it to prepare and preparation method and application
Technical field
The present invention relates to the preparation method and application of azole compounds and preparation method and the polymkeric substance utilizing it to prepare and polymkeric substance.
Background technology
The chemical property of Thienopyrroles derivative of really beginning one's study is that EnricBrillas etc. have studied 2 from 2000, the electrochemical behavior of 5 dithienyl pyrroles on Pt electrode; This Chane-Ching, L.Toppare and A.Cihaner etc. start a large amount of synthesizing new Thienopyrroles derivative, and have studied its photoelectrochemical behaviour in great detail.
The Polythiophene of bibliographical informations a large amount of at present and Polypyrrole derivatives are obtained by chemical oxidization method or electrochemical oxidation process, but, while oxidation of thiophene, pyrrole monomer, the peroxidation of polymkeric substance self can be caused again, although this phenomenon can be stopped by reduction oxidizing potential or strict controlled oxidization agent consumption, but their performance such as processing and optics can be caused to become poorer, and then limit their application.Therefore, recent years, increasing investigator starts the research and apply paying close attention to Thienopyrroles derivative.
Summary of the invention
The object of the invention is the problem that electrochromic polymer film-forming properties is poor, variable color is single that will solve existing existence, and the two Thienopyrroles compound of methylic triphenylamine base and preparation method and the polymkeric substance utilizing it to prepare and preparation method and application are provided.
The structural formula of the two Thienopyrroles compound of methylic triphenylamine base is:
The preparation method of the two Thienopyrroles compound of methylic triphenylamine base is prepared according to following steps:
One, 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer is synthesized:
1., by aluminum chloride be distributed in anhydrous methylene chloride, obtain the suspension liquid of aluminum chloride and anhydrous methylene chloride;
Step one 1. described in the amount of substance of aluminum chloride and the volume ratio of anhydrous methylene chloride be (0.06mol ~ 0.1mol): 30mL;
2., by the mixing solutions of thiophene and succinic chloride/methylene dichloride respectively with the rate of addition of 20/min ~ 30 droplet/min be added drop-wise to step one 1. in the aluminum chloride that obtains and anhydrous methylene chloride suspension liquid in, low whipping speed is stirring reaction 7h ~ 9h under 600r/min ~ 700r/min again, add ice again and massfraction is the hydrochloric acid of 35% ~ 37%, low whipping speed is stir 1.5h ~ 3h under 800r/min ~ 900r/min again, re-use separating funnel and isolate organic layer and water layer, discard water layer, functional quality mark is rare HCl and NaHCO of 35% ~ 37% successively 3organic layer is extracted, re-uses magnesium sulfate and carry out drying, re-use Rotary Evaporators and carry out revolving steaming, obtain solid matter A, dehydrated alcohol and ether is used to carry out cleaning 3 times ~ 5 times to solid A material respectively successively, again solid matter A is dissolved in methylene dichloride, re-use column chromatography method of purification to purify to solid matter A, re-use dehydrated alcohol and carry out recrystallization, obtain 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer,
Step one 2. described in thiophene and the volume ratio of suspension liquid of aluminum chloride and anhydrous methylene chloride be (4.8 ~ 5): 30;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride mixed by succinic chloride and methylene dichloride, and the volume ratio of succinic chloride and methylene dichloride is (2.7 ~ 3.0): 30;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride and the volume ratio of the suspension liquid of aluminum chloride and anhydrous methylene chloride be (2.5 ~ 3): 30;
Step one 2. described in the quality of ice and the volume ratio of thiophene be 50g:(4.8mL ~ 5mL);
Step one 2. described in massfraction be the hydrochloric acid of 35% ~ 37% and the volume ratio of thiophene be 5:(4.8 ~ 5);
Step one 2. described in column chromatography method of purification using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:1 in the mixed solution of described methylene dichloride and sherwood oil;
Two, N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is prepared:
1., 4-methyl-N is prepared, N-bis-(4-oil of mirbane) diamines:
In a nitrogen atmosphere open-chain crown ether is dissolved in dimethyl sulfoxide (DMSO), add p-fluoronitrobenzene and sodium hydride again, 20h ~ 24h is reacted under be 100 DEG C and stirring reaction being 800r/min ~ 900r/min in temperature again, then the yellow mercury oxide material that settles out in the distilled water pouring 0 DEG C ~ 5 DEG C into; Suction filtration is carried out to yellow mercury oxide material, obtains the yellow mercury oxide material after suction filtration; Use acetonitrile recrystallization is carried out to the yellow mercury oxide material after suction filtration, then at temperature is 40 DEG C ~ 50 DEG C dry 10h ~ 12h, obtain 4-methyl-N, N-bis-(4-oil of mirbane) diamines;
Step 2 1. described in the quality of open-chain crown ether and the volume ratio of dimethyl sulfoxide (DMSO) be (3g ~ 3.5g): 70mL;
Step 2 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be (3g ~ 9.0g): 70mL;
Step 2 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (0.3g ~ 1g): 70mL;
2., reduce:
By 4-methyl-N, N-bis-(4-oil of mirbane) diamines is dissolved into N, in N '-solvent dimethylformamide, add Pd/C catalyzer again, again hydrogen atmosphere, pressure be 8MPa ~ 10MPa, temperature be 70 DEG C and stirring velocity be 120r/min ~ 200r/min under stirring reaction 35h ~ 40h, then to be poured into temperature be that the distilled water of 0 DEG C ~ 5 DEG C settles out white precipitate material; Suction filtration is carried out to white sedimentable matter, obtains the white precipitate material after suction filtration; Use toluene recrystallization is carried out to the white precipitate material after suction filtration, then at temperature is 40 DEG C ~ 50 DEG C dry 10h ~ 12h, obtain N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines;
Step 2 2. described in 4-methyl-N, the quality of N-bis-(4-oil of mirbane) diamines and the volume ratio of N, N '-solvent dimethylformamide are (3g ~ 3.5g): 200mL;
Step 2 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Step 2 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-solvent dimethylformamide be (1g ~ 1.5g): 200mL;
Three, by 2,5-bis-(2-thiophene)-1,4-dimethyl diketone monomer, N '-(4-aminophenyl)-N '-p-methylphenyl-1,4 diamines and tosic acid join in toluene, reflux 3 days ~ 4 days at temperature is 110 DEG C ~ 120 DEG C again, be cooled to room temperature again, then carry out revolving steaming, obtain solid matter B; Again solid matter B is dissolved in methylene dichloride, then filters, then carry out revolving steaming, obtain solid matter C; Solid matter C is dissolved in methylene dichloride, re-uses column chromatography method of purification and solid matter C is purified, obtain yellow solid matter and be the two Thienopyrroles compound of methylic triphenylamine base;
Column chromatography method of purification described in step 3 is using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:5 in the mixed solution of described methylene dichloride and sherwood oil;
The mol ratio of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is 0.002:(0.0009 ~ 0.003);
The mol ratio of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and tosic acid is 0.002:(0.001 ~ 0.002);
The amount of substance of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and the volume ratio of toluene are (0.0015mol ~ 0.002mol): 100mL;
The structural formula of the two Thienopyrroles compound of the methylic triphenylamine base described in step 3 is
The structural formula utilizing the two Thienopyrroles compound of methylic triphenylamine base to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base is
the span of described n is 1≤n≤100.
The preparation method utilizing the two Thienopyrroles compound of methylic triphenylamine base to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base completes according to the following steps:
Two for methylic triphenylamine base Thienopyrroles compound and tetrabutylammonium perchlorate are dissolved into methylene dichloride, obtain the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate; Using ito glass as working electrode, platinum filament is comparison electrode, saturated Repone K electrode is reference electrode, the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate is as electrolytic solution, polymerization voltage be that 0.1V ~ 1.7V carries out polyreaction 5min ~ 10min, obtain polymeric film, be the two Thienopyrroles polymkeric substance of methylic triphenylamine base; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of the two Thienopyrroles compound of methylic triphenylamine base is 0.001mol/L; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of tetrabutylammonium perchlorate is 0.1mol/L ~ 0.15mol/L; The structural formula of the two Thienopyrroles polymkeric substance of described methylic triphenylamine base is
the span of described n is 1≤n≤100.
The two Thienopyrroles polymkeric substance of methylic triphenylamine base is applied in electrochromic material, opto-electronic device or biosensor as multi-functional organic polymer.
Advantage of the present invention:
One, the present invention extends the range of application of electrochromic material greatly, Polythiophene and polypyrrole are color developing and stability electrochromic material all preferably, and contain dimer or the tripolymer of heterocycle, as Thienopyrroles, its oxidizing potential can be reduced under the prerequisite not damaging its processing characteristics and optical property, obtain lower energy gap (Eg), and the electrochromic property of its polymkeric substance and film forming properties are all fine, so poly-two thiophene pyrrole derivative has the advantage of thiophene and pyrroles concurrently;
Having there are two oxidation peak at 0.65V, 0.95V place in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that two, prepared by the present invention, has occurred a reduction peak at 0.72V place;
Three, the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by the present invention has absorption peak at 425nm place, and when impressed voltage is from 0.0V to 1.5V, 404nm place absorption peak declines gradually, occurs new absorption peak and rise gradually at 515nm place; Electrochromic color finally becomes grey to purple from faint yellow again to blueness;
Uv-absorbing is there is in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that four, prepared by the present invention at 316nm and 414nm place;
Five, the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by the present invention starts greatly a large amount of weightless about 445 DEG C, and is significantly divided into two stages in Weight lose.First stage occurs between 445 DEG C to 640 DEG C, approximately weightlessness 40% ~ 41%; Subordinate phase occurs in 640 DEG C.
The present invention can obtain the two Thienopyrroles polymkeric substance of methylic triphenylamine base.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the two Thienopyrroles compound of methylic triphenylamine base prepared by embodiment one;
Fig. 2 is the hydrogen nuclear magnetic spectrogram of the two Thienopyrroles compound of methylic triphenylamine base prepared by embodiment one;
Fig. 3 is the partial enlarged drawing of Fig. 2;
Fig. 4 is the cyclic voltammogram of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two;
Fig. 5 is the chemical property figure in the two Thienopyrroles polymer reaction process of methylic triphenylamine base prepared by embodiment two;
Fig. 6 is the electrochromism figure of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two;
Fig. 7 is the uv absorption spectra of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two;
Fig. 8 is the thermal multigraph of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two.
Embodiment
Embodiment one: to be the structural formula of the two Thienopyrroles compound of methylic triphenylamine base be present embodiment:
Embodiment two: present embodiment is that the preparation method of the two Thienopyrroles compound of methylic triphenylamine base is prepared according to following steps:
One, 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer is synthesized:
1., by aluminum chloride be distributed in anhydrous methylene chloride, obtain the suspension liquid of aluminum chloride and anhydrous methylene chloride;
Step one 1. described in the amount of substance of aluminum chloride and the volume ratio of anhydrous methylene chloride be (0.06mol ~ 0.1mol): 30mL;
2., by the mixing solutions of thiophene and succinic chloride/methylene dichloride respectively with the rate of addition of 20/min ~ 30 droplet/min be added drop-wise to step one 1. in the aluminum chloride that obtains and anhydrous methylene chloride suspension liquid in, low whipping speed is stirring reaction 7h ~ 9h under 600r/min ~ 700r/min again, add ice again and massfraction is the hydrochloric acid of 35% ~ 37%, low whipping speed is stir 1.5h ~ 3h under 800r/min ~ 900r/min again, re-use separating funnel and isolate organic layer and water layer, discard water layer, functional quality mark is rare HCl and NaHCO of 35% ~ 37% successively 3organic layer is extracted, re-uses magnesium sulfate and carry out drying, re-use Rotary Evaporators and carry out revolving steaming, obtain solid matter A, dehydrated alcohol and ether is used to carry out cleaning 3 times ~ 5 times to solid A material respectively successively, again solid matter A is dissolved in methylene dichloride, re-use column chromatography method of purification to purify to solid matter A, re-use dehydrated alcohol and carry out recrystallization, obtain 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer,
Step one 2. described in thiophene and the volume ratio of suspension liquid of aluminum chloride and anhydrous methylene chloride be (4.8 ~ 5): 30;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride mixed by succinic chloride and methylene dichloride, and the volume ratio of succinic chloride and methylene dichloride is (2.7 ~ 3.0): 30;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride and the volume ratio of the suspension liquid of aluminum chloride and anhydrous methylene chloride be (2.5 ~ 3): 30;
Step one 2. described in the quality of ice and the volume ratio of thiophene be 50g:(4.8mL ~ 5mL);
Step one 2. described in massfraction be the hydrochloric acid of 35% ~ 37% and the volume ratio of thiophene be 5:(4.8 ~ 5);
Step one 2. described in column chromatography method of purification using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:1 in the mixed solution of described methylene dichloride and sherwood oil;
Two, N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is prepared:
1., 4-methyl-N is prepared, N-bis-(4-oil of mirbane) diamines:
In a nitrogen atmosphere open-chain crown ether is dissolved in dimethyl sulfoxide (DMSO), add p-fluoronitrobenzene and sodium hydride again, 20h ~ 24h is reacted under be 100 DEG C and stirring reaction being 800r/min ~ 900r/min in temperature again, then the yellow mercury oxide material that settles out in the distilled water pouring 0 DEG C ~ 5 DEG C into; Suction filtration is carried out to yellow mercury oxide material, obtains the yellow mercury oxide material after suction filtration; Use acetonitrile recrystallization is carried out to the yellow mercury oxide material after suction filtration, then at temperature is 40 DEG C ~ 50 DEG C dry 10h ~ 12h, obtain 4-methyl-N, N-bis-(4-oil of mirbane) diamines;
Step 2 1. described in the quality of open-chain crown ether and the volume ratio of dimethyl sulfoxide (DMSO) be (3g ~ 3.5g): 70mL;
Step 2 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be (3g ~ 9.0g): 70mL;
Step 2 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (0.3g ~ 1g): 70mL;
2., reduce:
By 4-methyl-N, N-bis-(4-oil of mirbane) diamines is dissolved into N, in N '-solvent dimethylformamide, add Pd/C catalyzer again, again hydrogen atmosphere, pressure be 8MPa ~ 10MPa, temperature be 70 DEG C and stirring velocity be 120r/min ~ 200r/min under stirring reaction 35h ~ 40h, then to be poured into temperature be that the distilled water of 0 DEG C ~ 5 DEG C settles out white precipitate material; Suction filtration is carried out to white sedimentable matter, obtains the white precipitate material after suction filtration; Use toluene recrystallization is carried out to the white precipitate material after suction filtration, then at temperature is 40 DEG C ~ 50 DEG C dry 10h ~ 12h, obtain N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines;
Step 2 2. described in 4-methyl-N, the quality of N-bis-(4-oil of mirbane) diamines and the volume ratio of N, N '-solvent dimethylformamide are (3g ~ 3.5g): 200mL;
Step 2 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Step 2 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-solvent dimethylformamide be (1g ~ 1.5g): 200mL;
Three, by 2,5-bis-(2-thiophene)-1,4-dimethyl diketone monomer, N '-(4-aminophenyl)-N '-p-methylphenyl-1,4 diamines and tosic acid join in toluene, reflux 3 days ~ 4 days at temperature is 110 DEG C ~ 120 DEG C again, be cooled to room temperature again, then carry out revolving steaming, obtain solid matter B; Again solid matter B is dissolved in methylene dichloride, then filters, then carry out revolving steaming, obtain solid matter C; Solid matter C is dissolved in methylene dichloride, re-uses column chromatography method of purification and solid matter C is purified, obtain yellow solid matter and be the two Thienopyrroles compound of methylic triphenylamine base;
Column chromatography method of purification described in step 3 is using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:5 in the mixed solution of described methylene dichloride and sherwood oil;
The mol ratio of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is 0.002:(0.0009 ~ 0.003);
The mol ratio of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and tosic acid is 0.002:(0.001 ~ 0.002);
The amount of substance of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and the volume ratio of toluene are (0.0015mol ~ 0.002mol): 100mL;
The structural formula of the two Thienopyrroles compound of the methylic triphenylamine base described in step 3 is
Embodiment three: the difference of present embodiment and embodiment two is: step one 1. described in the amount of substance of aluminum chloride and the volume ratio of anhydrous methylene chloride be 0.06mol:30mL.Other are identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two or three is: step one 2. described in thiophene and the volume ratio of suspension liquid of aluminum chloride and anhydrous methylene chloride be 4.8:30.Other are identical with embodiment two or three.
Embodiment five: the difference of one of present embodiment and embodiment two to four is: step one 2. described in the mixing solutions of succinic chloride/methylene dichloride and the volume ratio of the suspension liquid of aluminum chloride and anhydrous methylene chloride be 2.7:30.Other are identical with embodiment two to four.
Embodiment six: the difference of one of present embodiment and embodiment two to five is: step one 2. described in the quality of ice and the volume ratio of thiophene be 50g:4.8mL.Other are identical with embodiment two to five.
Embodiment seven: the difference of one of present embodiment and embodiment two to six is: step one 2. described in massfraction be the hydrochloric acid of 35% ~ 37% and the volume ratio of thiophene be 5:4.8.Other are identical with embodiment two to six.
Embodiment eight: to be the structural formula utilizing the two Thienopyrroles compound of methylic triphenylamine base to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base be present embodiment
the span of described n is 1≤n≤100.
The advantage of present embodiment:
One, present embodiment extends the range of application of electrochromic material greatly, Polythiophene and polypyrrole are color developing and stability electrochromic material all preferably, and contain dimer or the tripolymer of heterocycle, as Thienopyrroles, its oxidizing potential can be reduced under the prerequisite not damaging its processing characteristics and optical property, obtain lower energy gap (Eg), and the electrochromic property of its polymkeric substance and film forming properties are all fine, so poly-two thiophene pyrrole derivative has the advantage of thiophene and pyrroles concurrently;
Having there are two oxidation peak at 0.65V, 0.95V place in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that two, prepared by present embodiment, has occurred a reduction peak at 0.72V place;
Three, the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by present embodiment has absorption peak at 425nm place, and when impressed voltage is from 0.0V to 1.5V, 404nm place absorption peak declines gradually, occurs new absorption peak and rise gradually at 515nm place; Electrochromic color finally becomes grey to purple from faint yellow again to blueness;
Uv-absorbing is there is in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that four, prepared by present embodiment at 316nm and 414nm place;
Five, the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by present embodiment starts greatly a large amount of weightless about 445 DEG C, and is significantly divided into two stages in Weight lose.First stage occurs between 445 DEG C to 640 DEG C, approximately weightlessness 40% ~ 41%; Subordinate phase occurs in 640 DEG C.
The present invention can obtain the two Thienopyrroles polymkeric substance of methylic triphenylamine base.
Embodiment nine: present embodiment is that the preparation method utilizing the two Thienopyrroles compound of methylic triphenylamine base to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base completes according to the following steps:
Two for methylic triphenylamine base Thienopyrroles compound and tetrabutylammonium perchlorate are dissolved into methylene dichloride, obtain the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate; Using ito glass as working electrode, platinum filament is comparison electrode, saturated Repone K electrode is reference electrode, the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate is as electrolytic solution, polymerization voltage be that 0.1V ~ 1.7V carries out polyreaction 5min ~ 10min, obtain polymeric film, be the two Thienopyrroles polymkeric substance of methylic triphenylamine base; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of the two Thienopyrroles compound of methylic triphenylamine base is 0.001mol/L; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of tetrabutylammonium perchlorate is 0.1mol/L ~ 0.15mol/L; The structural formula of the two Thienopyrroles polymkeric substance of described methylic triphenylamine base is
the span of described n is 1≤n≤100.
The advantage of present embodiment:
One, present embodiment extends the range of application of electrochromic material greatly, Polythiophene and polypyrrole are color developing and stability electrochromic material all preferably, and contain dimer or the tripolymer of heterocycle, as Thienopyrroles, its oxidizing potential can be reduced under the prerequisite not damaging its processing characteristics and optical property, obtain lower energy gap (Eg), and the electrochromic property of its polymkeric substance and film forming properties are all fine, so poly-two thiophene pyrrole derivative has the advantage of thiophene and pyrroles concurrently;
Having there are two oxidation peak at 0.65V, 0.95V place in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that two, prepared by present embodiment, has occurred a reduction peak at 0.72V place;
Three, the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by present embodiment has absorption peak at 425nm place, and when impressed voltage is from 0.0V to 1.5V, 404nm place absorption peak declines gradually, occurs new absorption peak and rise gradually at 515nm place; Electrochromic color finally becomes grey to purple from faint yellow again to blueness;
Uv-absorbing is there is in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that four, prepared by present embodiment at 316nm and 414nm place;
Five, the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by present embodiment starts greatly a large amount of weightless about 445 DEG C, and is significantly divided into two stages in Weight lose.First stage occurs between 445 DEG C to 640 DEG C, approximately weightlessness 40% ~ 41%; Subordinate phase occurs in 640 DEG C.
The present invention can obtain the two Thienopyrroles polymkeric substance of methylic triphenylamine base.
Embodiment ten: present embodiment is that the two Thienopyrroles polymkeric substance of methylic triphenylamine base is applied in electrochromic material, opto-electronic device or biosensor as multi-functional organic polymer.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: the preparation method of the two Thienopyrroles compound of methylic triphenylamine base is prepared according to following steps:
One, 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer is synthesized:
1., by 0.006mol aluminum chloride be distributed in 30mL anhydrous methylene chloride, obtain the suspension liquid of aluminum chloride and anhydrous methylene chloride;
2., by the mixing solutions of 4.8mL thiophene, 2.7mL succinic chloride/methylene dichloride respectively with the rate of addition of 30/min be added drop-wise to 30mL step one 1. in the aluminum chloride that obtains and anhydrous methylene chloride suspension liquid in, low whipping speed is stirring reaction 7h under 700r/min again, add 50g ice again and 5mL massfraction is the hydrochloric acid of 37%, low whipping speed is stir 1.5h under 850r/min again, re-use separating funnel and isolate organic layer and water layer, discard water layer, successively
Functional quality mark is rare HCl and NaHCO of 37% 3extract, re-use magnesium sulfate and carry out drying, re-use Rotary Evaporators and carry out revolving steaming, obtain solid matter A; Dehydrated alcohol and ether is used to carry out cleaning 4 times to solid A material respectively, again solid matter A is dissolved in methylene dichloride, re-use column chromatography method of purification to purify to solid matter A, re-use dehydrated alcohol and carry out recrystallization, obtain 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride mixed by succinic chloride and methylene dichloride, and the volume ratio of succinic chloride and methylene dichloride is 3:30;
Step one 2. described in column chromatography method of purification using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:1 in the mixed solution of described methylene dichloride and sherwood oil; Two, N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is prepared:
1., 4-methyl-N is prepared, N-bis-(4-oil of mirbane) diamines:
In a nitrogen atmosphere 3.001g open-chain crown ether is dissolved in 70mL dimethyl sulfoxide (DMSO), add 3.001g p-fluoronitrobenzene and 0.5586g sodium hydride again, 20h is reacted under be 100 DEG C and stirring reaction being 900r/min in temperature again, then the yellow mercury oxide material that settles out in the distilled water pouring 2 DEG C into; Suction filtration is carried out to yellow mercury oxide material, obtains the yellow mercury oxide material after suction filtration; Use acetonitrile recrystallization is carried out to the yellow mercury oxide material after suction filtration, then at temperature is 50 DEG C dry 10h, obtain 4-methyl-N, N-bis-(4-oil of mirbane) diamines;
2., reduce:
By 3.0100g4-methyl-N, N-bis-(4-oil of mirbane) diamines is dissolved into 200mLN, in N '-solvent dimethylformamide, add 1.0615gPd/C catalyzer again, again hydrogen atmosphere, pressure be 8MPa, temperature be 70 DEG C and stirring velocity be 120r/min under stirring reaction 40h, then to be poured into temperature be that the distilled water of 2 DEG C settles out white precipitate material; Suction filtration is carried out to white sedimentable matter, obtains the white precipitate material after suction filtration; Use toluene recrystallization is carried out to the white precipitate material after suction filtration, then at temperature is 50 DEG C dry 10h, obtain N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines;
Step 2 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Three, by 0.002mol2,5-bis-(2-thiophene)-1,4-dimethyl diketone monomer, 0.002molN '-(4-aminophenyl)-N '-p-methylphenyl-1,4 diamines and 0.001mol tosic acid join in 100mL toluene, reflux 3 days at temperature is 120 DEG C again, be cooled to room temperature again, then carry out revolving steaming, obtain solid matter B; Again solid matter B is dissolved in methylene dichloride, then filters, then carry out revolving steaming, obtain solid matter C; Solid matter C is dissolved in methylene dichloride, re-uses column chromatography method of purification and solid matter C is purified, obtain yellow solid matter and be the two Thienopyrroles compound of methylic triphenylamine base;
Column chromatography method of purification described in step 3 is using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:5 in the mixed solution of described methylene dichloride and sherwood oil.
Chemical equation in embodiment one step one is:
Chemical equation in embodiment one step 2 is:
Chemical equation in embodiment one step 3 is:
The structural formula of the two Thienopyrroles compound of methylic triphenylamine base prepared by embodiment one is in structural formula 1,2,3,4,5,6,7,8 and 9 represents the hydrogen on different carbon atom;
Fig. 1 is the infrared spectrum of the two Thienopyrroles compound of methylic triphenylamine base prepared by embodiment one;
As can be seen from Figure 1, this infrared spectrum there is no amino at 3300 ~ 3500cm -1the charateristic avsorption band at place, N is described, two amino groups total overall reaction on N-bis-(4-aminomethyl phenyl)-N, N-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine, at 2900cm -1neighbouring peak is the stretching vibration of the methyl be connected with phenyl ring, at 1380cm -1and 1430cm -1near be the formation vibration of methyl, at 3010cm -1the characteristic peak at place is unsaturated hydrocarbon stretching vibration on thiophene, at 1397cm -1left and right is the stretching vibration of thiphene ring.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of the two Thienopyrroles compound of methylic triphenylamine base prepared by embodiment one;
Fig. 3 is the partial enlarged drawing of Fig. 2;
From Fig. 2 and Fig. 3, 1h-NMR (DMSO, TMS): the nuclear-magnetism peak at δ=2.31ppm place is the characteristic peak of methyl, the nuclear-magnetism peak at δ=5.01-8.01 place is the H nuclear-magnetism displacement on phenyl ring, the two ratio is about 1:10, close with theoretical value, can think that embodiment one has synthesized the two Thienopyrroles compound of methylic triphenylamine base.
Embodiment two: the preparation method that the two Thienopyrroles compound of the methylic triphenylamine base utilizing embodiment one to prepare prepares the two Thienopyrroles polymkeric substance of methylic triphenylamine base completes according to the following steps:
Two for methylic triphenylamine base Thienopyrroles compound and tetrabutylammonium perchlorate are dissolved into methylene dichloride, obtain the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate; Using ito glass as working electrode, platinum filament is comparison electrode, saturated Repone K electrode is reference electrode, the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate is as electrolytic solution, polymerization voltage be that 0.1V ~ 1.7V carries out polyreaction 10min, obtain polymeric film, be the two Thienopyrroles polymkeric substance of methylic triphenylamine base; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of the two Thienopyrroles compound of methylic triphenylamine base is 0.001mol/L; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of tetrabutylammonium perchlorate is 0.1mol/L.
The structural formula of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two is the span of described n is: 10≤n < 20.
Reaction formula in embodiment two is:
Fig. 4 is the cyclic voltammogram of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two; As can be seen from Figure 4, there are two oxidation peak at 0.65V, 0.95V place, occur a reduction peak at 0.72V place.
Fig. 5 is the chemical property figure in the two Thienopyrroles polymer reaction process of methylic triphenylamine base prepared by embodiment two;
As can be seen from Figure 5, first lap scanning has an obvious oxidation peak, and corresponding oxidizing potential is 1.01V, and this cyclic voltammetry result and known references report difference, and its reason introduces triaryl amine to create impact to potential; From the second circle, have a new oxidation peak at 0.80V, this oxidation peak owing to polymkeric substance oxide deposition on ito glass; Under repeatedly scan round, the current density at redox peak is more and more higher and deposit to electrode surface, obtains the two Thienopyrroles polymkeric substance of methylic triphenylamine base of electricity activation.
Fig. 6 is the electrochromism figure of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two;
As can be seen from Figure 6, before not executing voltage, the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two has absorption peak at 425nm place, when impressed voltage is from 0.0V to 1.5V, 404nm place absorption peak declines gradually, occurs new absorption peak and rise gradually at 515nm place; Electrochromic color finally becomes grey to purple from faint yellow again to blueness.
Fig. 7 is the uv absorption spectra of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two;
As can be seen from Figure 7, there is uv-absorbing at 316nm and 414nm place in the two Thienopyrroles polymkeric substance of methylic triphenylamine base that prepared by embodiment two.
Fig. 8 is the thermal multigraph of the two Thienopyrroles polymkeric substance of methylic triphenylamine base prepared by embodiment two, and as can be seen from Figure 8, polymkeric substance starts greatly a large amount of weightless about 445 DEG C, and is significantly divided into two stages in Weight lose.First stage occurs between 445 DEG C to 640 DEG C, approximately weightlessness 40% ~ 41%; Subordinate phase occurs in 640 DEG C.

Claims (10)

1. the two Thienopyrroles compound of methylic triphenylamine base, is characterized in that the structural formula of the two Thienopyrroles compound of methylic triphenylamine base is:
2. the preparation method of the two Thienopyrroles compound of methylic triphenylamine base, is characterized in that the preparation method of the two Thienopyrroles compound of methylic triphenylamine base is prepared according to following steps:
One, 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer is synthesized:
1., by aluminum chloride be distributed in anhydrous methylene chloride, obtain the suspension liquid of aluminum chloride and anhydrous methylene chloride;
Step one 1. described in the amount of substance of aluminum chloride and the volume ratio of anhydrous methylene chloride be (0.06mol ~ 0.1mol): 30mL;
2., by the mixing solutions of thiophene and succinic chloride/methylene dichloride respectively with the rate of addition of 20/min ~ 30 droplet/min be added drop-wise to step one 1. in the aluminum chloride that obtains and anhydrous methylene chloride suspension liquid in, low whipping speed is stirring reaction 7h ~ 9h under 600r/min ~ 700r/min again, add ice again and massfraction is the hydrochloric acid of 35% ~ 37%, low whipping speed is stir 1.5h ~ 3h under 800r/min ~ 900r/min again, re-use separating funnel and isolate organic layer and water layer, discard water layer, functional quality mark is rare HCl and NaHCO of 35% ~ 37% successively 3organic layer is extracted, re-uses magnesium sulfate and carry out drying, re-use Rotary Evaporators and carry out revolving steaming, obtain solid matter A, dehydrated alcohol and ether is used to carry out cleaning 3 times ~ 5 times to solid A material respectively successively, again solid matter A is dissolved in methylene dichloride, re-use column chromatography method of purification to purify to solid matter A, re-use dehydrated alcohol and carry out recrystallization, obtain 2,5-bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer,
Step one 2. described in thiophene and the volume ratio of suspension liquid of aluminum chloride and anhydrous methylene chloride be (4.8 ~ 5): 30;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride mixed by succinic chloride and methylene dichloride, and the volume ratio of succinic chloride and methylene dichloride is (2.7 ~ 3.0): 30;
Step one 2. described in the mixing solutions of succinic chloride/methylene dichloride and the volume ratio of the suspension liquid of aluminum chloride and anhydrous methylene chloride be (2.5 ~ 3): 30;
Step one 2. described in the quality of ice and the volume ratio of thiophene be 50g:(4.8mL ~ 5mL);
Step one 2. described in massfraction be the hydrochloric acid of 35% ~ 37% and the volume ratio of thiophene be 5:(4.8 ~ 5);
Step one 2. described in column chromatography method of purification using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:1 in the mixed solution of described methylene dichloride and sherwood oil;
Two, N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is prepared:
1., 4-methyl-N is prepared, N-bis-(4-oil of mirbane) diamines:
In a nitrogen atmosphere open-chain crown ether is dissolved in dimethyl sulfoxide (DMSO), add p-fluoronitrobenzene and sodium hydride again, 20h ~ 24h is reacted under be 100 DEG C and stirring reaction being 800r/min ~ 900r/min in temperature again, then the yellow mercury oxide material that settles out in the distilled water pouring 0 DEG C ~ 5 DEG C into; Suction filtration is carried out to yellow mercury oxide material, obtains the yellow mercury oxide material after suction filtration; Use acetonitrile recrystallization is carried out to the yellow mercury oxide material after suction filtration, then at temperature is 40 DEG C ~ 50 DEG C dry 10h ~ 12h, obtain 4-methyl-N, N-bis-(4-oil of mirbane) diamines;
Step 2 1. described in the quality of open-chain crown ether and the volume ratio of dimethyl sulfoxide (DMSO) be (3g ~ 3.5g): 70mL;
Step 2 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be (3g ~ 9.0g): 70mL;
Step 2 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (0.3g ~ 1g): 70mL;
2., reduce:
By 4-methyl-N, N-bis-(4-oil of mirbane) diamines is dissolved into N, in N '-solvent dimethylformamide, add Pd/C catalyzer again, again hydrogen atmosphere, pressure be 8MPa ~ 10MPa, temperature be 70 DEG C and stirring velocity be 120r/min ~ 200r/min under stirring reaction 35h ~ 40h, then to be poured into temperature be that the distilled water of 0 DEG C ~ 5 DEG C settles out white precipitate material; Suction filtration is carried out to white sedimentable matter, obtains the white precipitate material after suction filtration; Use toluene recrystallization is carried out to the white precipitate material after suction filtration, then at temperature is 40 DEG C ~ 50 DEG C dry 10h ~ 12h, obtain N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines;
Step 2 2. described in 4-methyl-N, the quality of N-bis-(4-oil of mirbane) diamines and the volume ratio of N, N '-solvent dimethylformamide are (3g ~ 3.5g): 200mL;
Step 2 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Step 2 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-solvent dimethylformamide be (1g ~ 1.5g): 200mL;
Three, by 2,5-bis-(2-thiophene)-1,4-dimethyl diketone monomer, N '-(4-aminophenyl)-N '-p-methylphenyl-1,4 diamines and tosic acid join in toluene, reflux 3 days ~ 4 days at temperature is 110 DEG C ~ 120 DEG C again, be cooled to room temperature again, then carry out revolving steaming, obtain solid matter B; Again solid matter B is dissolved in methylene dichloride, then filters, then carry out revolving steaming, obtain solid matter C; Solid matter C is dissolved in methylene dichloride, re-uses column chromatography method of purification and solid matter C is purified, obtain yellow solid matter and be the two Thienopyrroles compound of methylic triphenylamine base;
Column chromatography method of purification described in step 3 is using the mixed solution of methylene dichloride and sherwood oil as eluent; And the volume ratio of methylene dichloride and sherwood oil is 1:5 in the mixed solution of described methylene dichloride and sherwood oil;
The mol ratio of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and N '-(4-aminophenyl)-N '-p-methylphenyl-Isosorbide-5-Nitrae diamines is 0.002:(0.0009 ~ 0.003);
The mol ratio of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and tosic acid is 0.002:(0.001 ~ 0.002);
The amount of substance of 2,5-described in step 3 bis-(2-thiophene)-Isosorbide-5-Nitrae-dimethyl diketone monomer and the volume ratio of toluene are (0.0015mol ~ 0.002mol): 100mL;
The structural formula of the two Thienopyrroles compound of the methylic triphenylamine base described in step 3 is
3. the preparation method of the two Thienopyrroles compound of methylic triphenylamine base according to claim 2, is characterized in that the amount of substance of the aluminum chloride described in step one 1. and the volume ratio of anhydrous methylene chloride are 0.06mol:30mL.
4. the preparation method of the two Thienopyrroles compound of methylic triphenylamine base according to claim 2, is characterized in that the volume ratio of the suspension liquid of the thiophene described in step one 2. and aluminum chloride and anhydrous methylene chloride is 4.8:30.
5. the preparation method of the two Thienopyrroles compound of methylic triphenylamine base according to claim 2, is characterized in that the volume ratio of the mixing solutions of the succinic chloride/methylene dichloride described in step one 2. and the suspension liquid of aluminum chloride and anhydrous methylene chloride is 2.7:30.
6. the preparation method of the two Thienopyrroles compound of methylic triphenylamine base according to claim 2, is characterized in that the quality of the ice described in step one 2. and the volume ratio of thiophene are 50g:4.8mL.
7. the preparation method of the two Thienopyrroles compound of methylic triphenylamine base according to claim 2, is characterized in that the massfraction described in step one be 2. the hydrochloric acid of 35% ~ 37% and the volume ratio of thiophene is 5:4.8.
8. utilize the two Thienopyrroles compound of the methylic triphenylamine base described in claim 1 to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base, it is characterized in that the structural formula utilizing the two Thienopyrroles compound of methylic triphenylamine base to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base is
the span of described n is 1≤n≤100.
9. utilize the two Thienopyrroles compound of the methylic triphenylamine base described in claim 1 to prepare the preparation method of the two Thienopyrroles polymkeric substance of methylic triphenylamine base, it is characterized in that the preparation method utilizing the two Thienopyrroles compound of methylic triphenylamine base to prepare the two Thienopyrroles polymkeric substance of methylic triphenylamine base completes according to the following steps:
Two for methylic triphenylamine base Thienopyrroles compound and tetrabutylammonium perchlorate are dissolved into methylene dichloride, obtain the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate; Using ito glass as working electrode, platinum filament is comparison electrode, saturated Repone K electrode is reference electrode, the dichloromethane solution of the two Thienopyrroles compound of methylic triphenylamine base and tetrabutylammonium perchlorate is as electrolytic solution, polymerization voltage be that 0.1V ~ 1.7V carries out polyreaction 5min ~ 10min, obtain polymeric film, be the two Thienopyrroles polymkeric substance of methylic triphenylamine base; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of the two Thienopyrroles compound of methylic triphenylamine base is 0.001mol/L; In the dichloromethane solution of the two Thienopyrroles compound of described methylic triphenylamine base and tetrabutylammonium perchlorate, the concentration of tetrabutylammonium perchlorate is 0.1mol/L ~ 0.15mol/L; The structural formula of the two Thienopyrroles polymkeric substance of described methylic triphenylamine base is
the span of described n is 1≤n≤100.
10. the application of the two Thienopyrroles polymkeric substance of methylic triphenylamine base, is characterized in that the two Thienopyrroles polymkeric substance of methylic triphenylamine base is applied in electrochromic material, opto-electronic device or biosensor as multi-functional organic polymer.
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SOFIA TELITEL，等: "Thiophene Derivatives with Donor–π –Acceptor Structures for Enhanced Light-Absorption Properties and Efficient Cationic Polymerization upon Green-Light Irradiation", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 *

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