CN103159781A - Monomer and polymer of carboxyl-functionalized (3,4-ethylenedioxythiophene) and preparation method thereof - Google Patents
Monomer and polymer of carboxyl-functionalized (3,4-ethylenedioxythiophene) and preparation method thereof Download PDFInfo
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- CN103159781A CN103159781A CN2013101030851A CN201310103085A CN103159781A CN 103159781 A CN103159781 A CN 103159781A CN 2013101030851 A CN2013101030851 A CN 2013101030851A CN 201310103085 A CN201310103085 A CN 201310103085A CN 103159781 A CN103159781 A CN 103159781A
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- VGKLVWTVCUDISO-UHFFFAOYSA-N Brc1c[s]cc1Br Chemical compound Brc1c[s]cc1Br VGKLVWTVCUDISO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a conducting polymer and a monomer of carboxyl-functionalized poly(3, 4-ethylenedioxythiophene) and a preparation method thereof. The method for synthesizing the polymer comprises the following steps of: carrying out six-step synthesis reaction to obtain a carboxyl-functionalized 3,4-ethylenedioxythiophene monomer by utilizing 3,4-dibromothiophene as a raw material; and then, by using dichloromethane as an electrolytic solution, the carboxyl-functionalized 3,4-ethylenedioxythiophene monomer as a polymerization raw material and tetrafluoroborate tetrabutyl ammonium as an electrolyte and selecting 1.3V as a deposition voltage, directly depositing on a platinum sheet so as to obtain a black carboxyl-functionalized poly(3,4-ethylenedioxythiophene) film. The chain of the polymer prepared by the method contains a carboxyl group, so that the polymer can be chemically crosslinked with substances containing active groups such as -NH2, -OH and -X (halogen), and composite materials with different performances can be obtained; and the polymer can be applied to decorate electrodes and used as a material for producing electrochemical sensors, and has a wide application prospect in the electrochemical detection field.
Description
Technical field
The invention belongs to the organic conductive macromolecule field, particularly (3,4-ethylene dioxythiophene) monomer of a kind of carboxyl-functional, polymkeric substance and preparation method thereof.
Background technology
Poly-(3,4-ethylene dioxythiophene) is (PEDOT) one of the most stable conductive polymers, since this material is synthesized to so far, because of its environmental stability with excellence, high conductivity (〉 10
2S/cm) and higher visible light transmissivity (〉 80%), caused people's extensive concern, be widely used in subsequently rechargeable battery, electrochromic display device, Organic Light Emitting Diode, ultracapacitor, antistatic coating, corrosion inhibitor, printed wiring smart window, microwave absorbing material, the fields such as chemical/biological sensors.
The conducting polymer field is developed so far, and synthetic novel conductive polymer with excellent properties is still the core in whole field.In conducting polymer family, EDOT derivative with active group is fewer, the synthetic EDOT derivatives monomer that contains different functional groups, for designing PEDOT derivative or the analogue of different performance, also provide new thinking for the performance of adjusting in this way or improve PEDOT simultaneously.At present, PEDOT derivative or the analogue of difference in functionality are produced out, and are widely applied to subsequently different fields.
Phenylformic acid is a kind of important acid type food preservatives, under acidic conditions, mould, yeast and bacterium is all had restraining effect, share in the adult skin mycosis treatment of mycotic infection of superficial part such as ringworm of the body, the tinea manuum and tinea pedis etc. with Whitfield's ointment.
Summary of the invention
The purpose of this invention is to provide (3,4-ethylene dioxythiophene) monomer, polymkeric substance of a kind of carboxyl-functional and preparation method thereof.
(3,4-ethylene dioxythiophene) monomer of carboxyl-functional of the present invention, its structural formula is as follows:
Title is abbreviated as: EDOT-Ph-COOH.
(3,4-ethylene dioxythiophene) conductive polymers of carboxyl-functional of the present invention, its structural formula is as follows:
Title is abbreviated as: PEDOT-Ph-COOH.
The synthetic method of (3,4-ethylene dioxythiophene) monomer of carboxyl-functional of the present invention is: (1), be starting raw material with 3,4-dibromo thiophene, in sodium methoxide solution, take cupric oxide and potassiumiodide as catalyzer, use the methoxy substitution bromine; (2), tosic acid (
p-TSA) under catalysis, prepare chloromethyl EDOT (EDOT-MeCl) with the cyclization of 3-chlorine-1,2-propylene glycol; (3), with the sodium-acetate esterification after hydrolysis prepare methylol EDOT (EDOT-MeOH); (4), be hydrolyzed the EDOT monomer (EDOT-Ph-COOH) of preparing carboxyl-functional after EDOT-MeOH and 4-bromomethyl-benzoic acid ethyl ester etherificate in NaOH solution.
(3 of carboxyl-functional of the present invention; the 4-ethylenedioxy thiophene) preparation method of conductive polymers is: take above-mentioned EDOT-Ph-COOH as raw material; methylene dichloride is as electrolytic solution; tetrafluoride boron TBuA is ionogen, stirs after logical argon shield, adopts three-electrode system under room temperature; take platinum filament as reference electrode; stainless steel substrates is supporting electrode and platinized platinum working electrode, applies constant voltage 1.3 V, obtains the polymer P EDOT-Ph-COOH of black at electrode surface.
(3 of carboxyl-functional of the present invention, the 4-ethylenedioxy thiophene) monomer and its polymkeric substance, because it has this active group of carboxyl, be conducive to method by chemically crosslinked in conjunction with different bioactive molecules or material, make in the first-class research field of the immobilization of chemical/biological sensing device, photoelectric material, biomolecules to have broad application prospects, that its preparation method has is with low cost, technique is simple, the advantage such as easy and simple to handle.
Description of drawings
Fig. 1 is the structural formula of carboxyl-functional of the present invention (3,4-ethylene dioxythiophene) monomer.
Fig. 2 is the structural formula of carboxyl-functional of the present invention (3,4-ethylene dioxythiophene) conductive polymers.
Fig. 3 is the cyclic voltammetric collection of illustrative plates of EDOT-Ph-COOH monomer of the present invention electrochemical polymerization.
Fig. 4 is the cyclic voltammetric collection of illustrative plates of PEDOT-Ph-COOH film of the present invention.
Fig. 5 is the adulterate infared spectrum of attitude of the doping attitude of monomer of the present invention, polymkeric substance and going.
Fig. 6 is the adulterate uv-spectrogram of attitude of the doping attitude and going of polymkeric substance of the present invention.
Fig. 7 is the adulterate fluorescence pattern of attitude of the doping attitude and going of polymkeric substance of the present invention.
Embodiment
Embodiment 1: monomeric compound EDOT-Ph-COOH's is synthetic
Monomer EDOT-Ph-COOH synthetic schemes is as follows:
Concrete synthesis step is as described below:
1,3,4-dimethoxy-thiophene synthetic:
At N
2Under protection; with 3; 4-dibromo thiophene (30 g; 124.00 mmol); cupric oxide (9.86 g, 123.95 mmol) and potassiumiodide (0.84 g, 5.06 mmol) join in 1000 mL there-necked flasks; adding mass fraction is 30% sodium methoxide solution (123.26 g, 684.52 mmol) and 150 mL methyl alcohol.Return stirring three days, the TLC monitoring reaction is complete, and reaction solution is cooled to room temperature and filters, and uses the methanol wash filter cake.Filtrate is poured into water.Use dichloromethane extraction, merge the organic phase anhydrous sodium sulfate drying, the desolventizing of decompression rotary evaporation, silica gel column chromatography (sherwood oil) separates, and gets colourless oil liquid (26.20 g, 109.02 mmol);
Productive rate: 88.02%;
1H?NMR?(400?MHz,?CDCl
3):?δ6.19?(s,?2H),?3.86?(s,?6H)。
2, EDOT-MeCl's is synthetic:
At N
2Under protection, with 3,4-dimethoxy-thiophene (16.30 g, 113.05 mmol), 3-chloro-1,2-glycol (25.62 g, 231.77 mmol) and tosic acid (1.6 g, 9.29 mmol) are dissolved in 280 mL dry toluenes, are heated to 90
oThen C stirring reaction 24 h add 3-chloro-1, and 2-glycol (25.62 g, 231.77 mmol) continues reaction 3 h.Be cooled to room temperature, filter with being added with diatomaceous Büchner funnel, the toluene wash filter cake, the desolventizing of organic phase decompression rotary evaporation, silica gel column chromatography (sherwood oil) separates, and obtains white solid (13.35 g, 70.03 mmol);
Productive rate: 61.96%;
1H?NMR?(400?MHz,?CDCl
3):?δ6.37?(s,?2H),?4.35-4.40?(m,?1H),?4.27-4.35?(m,?1H),?4.14-4.18?(m,?1H),?3.65-3.75?(m,?2H)。
3, EDOT-MeOH's is synthetic:
At N
2Under protection, with EDOT-MeCl(3.82 g, 20.04 mmol), sodium-acetate (2.50 g, 30.46 mmol) is dissolved in 60 mL dimethyl sulfoxide (DMSO).Be heated to 110
oC～115
oThe C stirring reaction is 1.5 h approximately, and the TLC monitoring reaction is complete.Washing, the concentrated organic phase of extraction, anhydrous sodium sulfate drying.Filter, filtrate is revolved the steaming desolventizing, and silica gel column chromatography (sherwood oil) separates, and gets pale yellow oily liquid body (3.82 g, 17.84 mmol);
Productive rate: 88.84%.
4, EDOT-MeOH's is synthetic:
Add EDOT-MeOOAc(3.25 g in there-necked flask, 15.16 mmol), sodium hydroxide (2.38 g, 59.5 mmol) and 70 mL water, reflux, the TLC monitoring reaction is complete, is cooled to room temperature.Use dichloromethane extraction, merge organic phase, use anhydrous sodium sulfate drying, filter, the desolventizing of decompression rotary evaporation, (sherwood oil: ethyl acetate=4:1) separate gets product (577.69 mg, 12.84 mmol) to silica gel column chromatography;
Productive rate: 84.80%;
1H?NMR?(400?MHz,?CDCl
3):?δ6.34?(s,?2H),?4.24?(d,?2H),?4.07-4.12?(m,?1H),?3.84-3.87?(m,?2H)。
5, EDOT-Ph-COOC
2H
5Synthetic:
At N
2Protection under condition of ice bath, adds EDOT-MeOH(1.72 g, 10 mmol in there-necked flask) and the anhydrous THF of 20 mL, subsequently at N
2Add KI(332 mg under atmosphere, 2 mmol) and NaH (60%, 560 mg, 14 mmol), after stirring for some time, dropwise add 4-bromomethyl-benzoic acid ethyl ester (3.40 g that are dissolved in the 20 anhydrous THF of mL, 14 mmol), after at room temperature stirring for some time, reflux is spent the night.The TLC monitoring reaction is complete, is cooled to room temperature.Layering is processed in water and ethyl acetate, merges organic phase, uses anhydrous sodium sulfate drying, filter, and the desolventizing of decompression rotary evaporation, (sherwood oil: ethyl acetate=9:1) separate gets product (0.58 g, 1.73 mmol) to silica gel column chromatography;
Productive rate: 86.38%;
1H?NMR?(400?MHz,?CDCl
3):?δ8.06?(d,?2H),?7.42?(d,?2H),?6.41?(s,?2H),?4.67(s,?2H),?4.48-4.42?(m,1H),?4.32?(d,?2H),?4.16-4.19?(m,?2H),?3.80-3.84?(m,?2H),?1.45-1.48?(m,?3H)。
6, EDOT-Ph-COOH's is synthetic:
Add EDOT-Ph-COOH(3.25 g in there-necked flask, 9.72 mmol), sodium hydroxide (6.4 g, 1.6 mol) and 80 mL water, reflux, the TLC monitoring reaction is complete, is cooled to room temperature.Regulate pH＜3 with HCl, use ethyl acetate extraction, merge organic phase, use anhydrous sodium sulfate drying, filter, the desolventizing of decompression rotary evaporation, (sherwood oil: ethyl acetate=1:1) separate gets product (2.78 g, 9.08 mmol) to silica gel column chromatography;
Productive rate: 93.52%;
1H?NMR?(400?MHz,?CDCl
3):?δ8.12?(d,?2H),?7.46?(d,?2H),?6.36?(s,?2H),?4.39-4.37?(m,?1H),?4.32?(d,?2H),?4.30-4.26?(m,?2H),?3.78-3.70?(m,?2H)。
Embodiment 2: the electrochemical synthesis of polymer P EDOT-Ph-COOH
Take refining methylene dichloride as electrolytic solution, concentration is 0.02 mol L
-1EDOT-Ph-COOH is polymerization single polymerization monomer, 0.1 mol L
-1Tetrafluoride boron TBuA be ionogen.Stir, continue to pass into argon shield after 20 minutes, keep solution under argon atmosphere.Take platinized platinum as working electrode, stainless steel substrates is to electrode, and platinum filament is reference electrode, constant potential polymerization in three-electrode system.The polymerization potential of polymkeric substance is at 1.13 V as can be known from Fig. 3 illustration, so the current potential that applies work during the constant potential polymerization of film is 1.30 V, can obtain the solid of black.Fig. 3 can see that a pair of obvious redox peak can appear in the polymerization process of this monomer.
The properties and characterization of PEDOT-Ph-COOH: Fig. 4 can see that the class rectangle appears in polymer P EDOT-Ph-COOH unlike PEDOT, but a pair of obvious redox peak is arranged, corresponding oxidation peak current and reduction peak current all with sweep speed good linear relationship arranged, illustrate that this polymkeric substance has good redox characteristic.In addition, the adulterate polymer architecture of attitude of the monomer of acquisition, doping attitude and going characterizes as shown in Figure 5 infared spectrum, uv-spectrogram shown in Figure 6, fluorescence pattern shown in Figure 7.
Claims (5)
1. (3,4-ethylene dioxythiophene) monomer of a carboxyl-functional, it is characterized in that: its structural formula is:
。
2. (3,4-ethylene dioxythiophene) conductive polymers of a carboxyl-functional, it is characterized in that: its structural formula is:
3. (3,4-ethylene dioxythiophene) monomer of carboxyl-functional as claimed in claim 1, its synthetic method is: (1), be starting raw material with 3,4-dibromo thiophene, in sodium methoxide solution, take cupric oxide and potassiumiodide as catalyzer, use the methoxy substitution bromine; (2), tosic acid (
p-TSA) under catalysis, prepare chloromethyl EDOT with the cyclization of 3-chlorine-1,2-propylene glycol; (3), with the sodium-acetate esterification after hydrolysis prepare methylol EDOT; (4), be hydrolyzed the EDOT monomer of preparing carboxyl-functional after EDOT-MeOH and 4-bromomethyl-benzoic acid ethyl ester etherificate in NaOH solution.
4. (3 of carboxyl-functional as claimed in claim 2; the 4-ethylenedioxy thiophene) conductive polymers; its synthetic method is: take EDOT-Ph-COOH as raw material, methylene dichloride is as electrolytic solution, and tetrafluoride boron TBuA is ionogen; stir after logical argon shield; adopt three-electrode system under room temperature, take platinum filament as reference electrode, stainless steel substrates is supporting electrode and platinized platinum working electrode; apply constant voltage 1.3 V, obtain the polymer P EDOT-Ph-COOH of black at electrode surface.
5. the application of (3,4-ethylene dioxythiophene) conductive polymers in the immobilization of chemical/biological sensing device, photoelectric material, biomolecules of carboxyl-functional as claimed in claim 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641843A (en) * | 2013-09-26 | 2014-03-19 | 南京工业大学 | Synthetic method for (3,4)-1,4- dioxo ethylidene thiophene-2'-methanol |
| CN108663412A (en) * | 2018-05-28 | 2018-10-16 | 上海大学 | A kind of sensor of chemical gas and preparation method thereof |
| CN109679071A (en) * | 2018-12-27 | 2019-04-26 | 大连理工大学 | A kind of novel PCLT-g-PEDOT electrically conductive composite and preparation method thereof |
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|---|---|---|---|---|
| US5111327A (en) * | 1991-03-04 | 1992-05-05 | General Electric Company | Substituted 3,4-polymethylenedioxythiophenes, and polymers and electro responsive devices made therefrom |
| WO2006073968A2 (en) * | 2004-12-30 | 2006-07-13 | E. I. Dupont De Nemours And Company | Derivatized 3,4-alkylenedioxythiophene monomers, methods of making them, and use thereof |
| CN102391284A (en) * | 2011-09-26 | 2012-03-28 | 江西科技师范学院 | Chiral poly (3,4-ethylenedioxythiophene) derivative monomer, polymer and preparation method thereof |
| JP2012153847A (en) * | 2011-01-28 | 2012-08-16 | Jsr Corp | New polymer compound and its intermediate |
-
2013
- 2013-03-28 CN CN2013101030851A patent/CN103159781A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5111327A (en) * | 1991-03-04 | 1992-05-05 | General Electric Company | Substituted 3,4-polymethylenedioxythiophenes, and polymers and electro responsive devices made therefrom |
| WO2006073968A2 (en) * | 2004-12-30 | 2006-07-13 | E. I. Dupont De Nemours And Company | Derivatized 3,4-alkylenedioxythiophene monomers, methods of making them, and use thereof |
| JP2012153847A (en) * | 2011-01-28 | 2012-08-16 | Jsr Corp | New polymer compound and its intermediate |
| CN102391284A (en) * | 2011-09-26 | 2012-03-28 | 江西科技师范学院 | Chiral poly (3,4-ethylenedioxythiophene) derivative monomer, polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YAO LU，等: "Electrosynthesis and characterization of poly(hydroxy-methylated-3,4-ethylenedioxythiophene) film in aqueous micellar solution and its biosensing application", 《CHINESE JOURNAL OF POLYMER SCIENCE》, vol. 30, no. 6, 30 November 2012 (2012-11-30), pages 824 - 836 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641843A (en) * | 2013-09-26 | 2014-03-19 | 南京工业大学 | Synthetic method for (3,4)-1,4- dioxo ethylidene thiophene-2'-methanol |
| CN108663412A (en) * | 2018-05-28 | 2018-10-16 | 上海大学 | A kind of sensor of chemical gas and preparation method thereof |
| CN109679071A (en) * | 2018-12-27 | 2019-04-26 | 大连理工大学 | A kind of novel PCLT-g-PEDOT electrically conductive composite and preparation method thereof |
| CN109679071B (en) * | 2018-12-27 | 2022-04-29 | 大连理工大学 | PCLT-g-PEDOT conductive compound and preparation method thereof |
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Application publication date: 20130619 |