CN102775423A - Method for preparing polymer monomer 3,4-ethylenedioxythiophene - Google Patents
Method for preparing polymer monomer 3,4-ethylenedioxythiophene Download PDFInfo
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- CN102775423A CN102775423A CN201210254379XA CN201210254379A CN102775423A CN 102775423 A CN102775423 A CN 102775423A CN 201210254379X A CN201210254379X A CN 201210254379XA CN 201210254379 A CN201210254379 A CN 201210254379A CN 102775423 A CN102775423 A CN 102775423A
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Abstract
The invention relates to a method for preparing polymer monomer 3,4-ethylenedioxythiophene. The method includes firstly dissolving ethyl chloroacetate and sodium sulphide in acetone to react to obtain diethyl thioglycolate; secondly, dissolving the diethyl thioglycolate to ethanol, adding sodium ethoxide and diethyl oxalate into the ethanol, heating and reflowing to obtain ethanol solution of 2,5-dioctyl phthalate ethyl ester-3,4-thiophene glycol sodium; thirdly, adding dichloroethane and tetrabutylammonium bromide into the ethanol solution of the 2,5-dioctyl phthalate ethyl ester-3,4-thiophene glycol sodium, heating and reflowing to obtain 3,4-ethylenedioxy-2,5-dioctyl phthalate ethyl ester thiophene; fourthly, dissolving the 3,4-ethylenedioxy-2,5-dioctyl phthalate ethyl ester thiophene in mixed solvent, adding sodium chloride, heating and reacting, and finally reducing pressure and rectifying. The method for preparing polymer monomer 3,4-ethylenedioxythiophene is few in procedures, low in cost, safe and reliable in technique, simple and fast in post-treatment method, and products are high in yield and purity.
Description
Technical field
The invention belongs to the preparation field of heterogeneous ring compound, particularly a kind of polymer materials monomer 3, the preparation method of 4-enedioxy thiophene.
Background technology
EDOT comes to light as medicine intermediate at first, and its polymer P EODT came to light as good macromolecule conducting material again afterwards, thus the epoch of having started macromolecule conducting material, and its discoverer is also authorized 2000 years Nobel chemistry Prizes.PEDOT has the electric conductivity height, the transparency is good, stability is high, be easy to multiple advantage such as processing; And be used for multiple fields such as organic thin film solar cell material, solid capacitor, electrically conductive ink, OLED material, electrochromic material, antistatic material, novel electromagnetic shielding material; And because its excellent characteristic; PEODT will be used in the research in field widely, and the increasing demand to this material monomer on the market increases.
3, the synthetic of 4-enedioxy thiophene (EDOT) just had five classical step synthesis methods of bibliographical information as far back as 1998, but because yield has only 25～30%, technology lacks innovation, and is comparatively backward.2004, Tetrahedron Letters, 45 (2004), 6049-6050 has reported up-to-date 3; 4-enedioxy thiophene (EDOT) compound method, with 2,3-dimethoxy-1,3-butadiene is as raw material; Through ring and the ether exchange that reaches a standard, obtain 3,4-enedioxy thiophene (EDOT).But 2,3-dimethoxy-1,3-butadiene market value is expensive, has increased the cost of technology greatly, is unfavorable for the control of cost, so this route only is used for breadboard methodology and explores, inconvenience is used for industrial production.Heterocycles in 2010,82 (1), 449-460; 2010 documents adopt butynediol, cylite and bromoethanol as raw material, through eight one step process, and synthetic the finished product 3,4-enedioxy thiophene (EDOT); The method that this piece document is used only is fit to laboratory method, wherein Lithium Aluminium Hydride and sodium hydrogen; All be comparatively dangerous industrial chemicals, be not suitable for suitability for industrialized production, and adopt the reaction of eight steps; Five-step approach than classical has caused higher cost, has increased the production cycle.Other one piece of patent Jpn.Kokai Tokkyo Koho in 2010; 2010132571,17 Jun 2010 are reported on the classical five-step approach and change, and adopt methyl chloroacetate and sodium sulphite as the synthetic the finished product 3 of raw material; 4-enedioxy thiophene (EDOT); Total recovery is 60%, but the temperature control link in this patent is more, also is not suitable for technology and amplifies.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polymer materials monomer 3, the preparation method of 4-enedioxy thiophene, the ingenious one kettle way that utilizes of this method; Route is short, and is with short production cycle, and synthetic cost is low; Synthesis technique is safe and reliable; Post-treating method is simple and convenient, and the yield of the product that obtains is high, and purity is high.
A kind of polymer materials monomer 3 of the present invention, the preparation method of 4-enedioxy thiophene comprises:
(1) the thiodiglycolic acid diethyl ester is synthetic
2:1 is dissolved in ethyl chloroacetate and sodium sulphite in the acetone in molar ratio, stirring at room 2 ~ 6 hours, and reaction finishes after-filtration, and solvent evaporated obtains the thiodiglycolic acid diethyl ester then; The thiodiglycolic acid diethyl ester crude product that obtains can directly be used for next step reaction, need not to be further purified;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic
Above-mentioned thiodiglycolic acid diethyl ester is dissolved in the ethanol, adds sodium ethylate under the room temperature, slowly add oxalic acid diethyl ester then; Reflux; After finishing, reaction obtains midbody 2,5-dioctyl phthalate ethyl ester-3, the ethanolic soln of 4-thiophene two sodium alkoxide; This solution can directly be used for next step reaction, need not any purifying; Wherein the mol ratio of sodium ethylate and ethyl chloroacetate is 2.0 ~ 2.2:1, and the mol ratio of oxalic acid diethyl ester and ethyl chloroacetate is 1.0 ~ 1.2:1;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic
At above-mentioned midbody 2,5-dioctyl phthalate ethyl ester-3 adds ethylene dichloride in the ethanolic soln of 4-thiophene two sodium alkoxide; Add phase-transfer catalyst again, reflux 4 ~ 8 hours is after reaction finishes; Boil off unnecessary ethanol and oxalic acid diethyl ester, add ETHYLE ACETATE, boil off ETHYLE ACETATE after the washing; Obtain midbody 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene;
Synthesizing of (4) 3,4-enedioxy thiophene (EDOT)
With above-mentioned midbody 3; 4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene are dissolved in the mixed solvent of DMSO 99.8MIN. and water composition, add decarboxylation reagent; Be heated to 115-130 ℃ of reaction 2-8 hour then; Rectification under vacuum after reaction finishes obtains colorless liquid product 3,4-enedioxy thiophene (EDOT).
The mol ratio of ethylene dichloride described in the step (3) and ethyl chloroacetate is 1.0 ~ 2.0:1.
Phase-transfer catalyst described in the step (3) is a Tetrabutyl amonium bromide.
The consumption of the phase-transfer catalyst described in the step (3) is 5 ~ 20% of an ethyl chloroacetate molar weight.
The volume ratio of DMSO 99.8MIN. and water is 1 ~ 5:1 in the mixed solvent described in the step (4).
Decarboxylation reagent described in the step (4) is sodium-chlor.
The consumption of the decarboxylation reagent described in the step (4) and the mol ratio of ethyl chloroacetate are 1.2 ~ 3.0:1.
Synthetic route of the present invention is following:
The sign of sintetics EDOT of the present invention:
Pass through proton nmr spectra below, mass spectrum, methods such as high resolution gas chromatography characterize synthetic compd E DOT of the present invention.
1, the proton nmr spectra data are following:
H-NMR(400MHz,CDCl3):δ=6.32(s,2H),4.19(s,4H).
C-NMR(400MHz,CDCl3):δ=141.6,99.5,64.5.
Wherein (s 2H) is thiophene fragrance ring hydrogen, 4.19 (s, 4H) hydrogen of two methylene radical between two Sauerstoffatoms in chemical shift δ=6.32.
The nuclear magnetic resonance measuring result confirms as 3,4-enedioxy thiophene (EDOT).
2, the mass spectrograph determination data is following:
ESI-MS(m/z,%)143。
This compound molecular weight is 142, and occurring 143 in the spectrogram is [M+H]
+Signal.The mass spectroscopy result confirms as a kind of novel polymer material monomer 3,4-enedioxy thiophene (EDOT).
3, high resolution gas chromatography:
Purity is 98 ~ 99%.
The above-mentioned proton nmr spectra of analysis-by-synthesis, mass spectrum, high resolution gas chromatography shows that synthetic the finished product of the present invention are 3,4-enedioxy thiophene (EDOT), and purity is qualified.Its structural formula is:
Wherein the total recovery of four-step reaction of the present invention is 57.6 ~ 67.2%.
The present invention is the most initial raw material with ethyl chloroacetate and sodium sulphite; Through sulfo-; Cyclisation and alkylation one kettle way; Decarboxylation prepares our needed product novel polymer material monomer 3 quickly and easily, 4-enedioxy thiophene (EDOT), and carry out data characterization through liquid chromatography, nuclear magnetic spectrogram, mass spectrum.The ingenious one kettle way that utilizes of technology of the present invention, route is short, and is with short production cycle, and synthetic cost is low, and synthesis technique is safe and reliable, and post-treating method is simple and convenient; The yield of product of the present invention high (being 57.6 ~ 67.2%), product purity high (being 98 ~ 99%).
Beneficial effect:
1, the present invention improves operational path on the basis of five step synthesis methods of original classics, has realized the one kettle way in second step and the 3rd step, and yield has been brought up to 72～80% from 40～50%; And last decarboxylation link, also shorten into a step from original two steps, not only shortened reaction time, also reduced the process of aftertreatment simultaneously, practiced thrift cost;
2, recovered solvent ethanol and DMSO 99.8MIN. can overlap easily and use next time in the reaction among the present invention, have reduced the discharging and the processing cost of toxic reagent, meet national environmental protection and call;
3, preparation method of the present invention has carried out depth optimization to the existing technology of EDOT, can realize this product scale operation, to satisfy the heavy demand of domestic and international market to EDOT;
4, preparing method's of the present invention yield is high, is 57.6 ~ 67.2%; Obtain 3, the purity of 4-enedioxy thiophene is high, is 98 ~ 99%; And in synthetic and production process, midbody and the finished product purity can both reach more than 95%, all can satisfy market demands.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) the thiodiglycolic acid diethyl ester is synthetic
With ethyl chloroacetate (245.2g, 2.0mol) be added drop-wise to sodium sulphite (78g, in acetone soln 1.0mol) (2L), stirring at room 2 hours generates the thiodiglycolic acid diethyl ester; After monitoring reaction finished, direct filtration, solvent evaporated obtained bullion 323 grams, directly are used for next step reaction, need not to be further purified;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic
Last one the step raw material (323g) is dissolved in (2L) in the ethanol, add under the room temperature in batches sodium ethylate (136g, 2mol); Slow adding oxalic acid diethyl ester (146g, 1mol), temperature rising reflux 4 hours; After monitoring reaction finishes, obtain midbody 2,5-dioctyl phthalate ethyl ester-3; The ethanolic soln of 4-thiophene two sodium alkoxide, this solution can directly be used for next step reaction, need not any purifying;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic
To in above-mentioned solution, add ethylene dichloride (99g, 1mol), add again the phase-transfer catalyst Tetrabutyl amonium bromide (16.1g, 5%mol); Reflux 4 hours after monitoring reaction finishes, boils off unnecessary ethanol, and oxalic acid diethyl ester; Add ETHYLE ACETATE,, boil off ETHYLE ACETATE, obtain midbody 3 with washing 3 times; 4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene 211.7g, yield 72%.
Synthesizing of (4) 3,4-enedioxy thiophene (EDOT)
With 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene (209g, (volume ratio is 2:1 0.73mol) to be dissolved in DMSO 99.8MIN. and water; 1.5L) in, (85.4g 1.46mol), is heated to 120 ℃ of reactions 4 hours to add sodium-chlor; After monitoring reaction finished, rectification under vacuum steamed DMSO 99.8MIN., water, by product ethyl formate and product 3,4-enedioxy thiophene (EDOT); Get EDOT 83g, yield 80%, product E DOT are colourless liquid.
Embodiment 2
(1) the thiodiglycolic acid diethyl ester is synthetic
With ethyl chloroacetate (245.2g, 2.0mol) be added drop-wise to sodium sulphite (78g, in acetone soln 1.0mol) (2L), stirring at room 4 hours generates the thiodiglycolic acid diethyl ester; After monitoring reaction finished, direct filtration, solvent evaporated obtained bullion 324 grams, directly are used for next step reaction, need not to be further purified;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic
Last one the step raw material (324g) is dissolved in (2L) in the ethanol, add under the room temperature in batches sodium ethylate (150g, 2.2mol); Slow adding oxalic acid diethyl ester (146g, 1mol), temperature rising reflux 4 hours; After monitoring reaction finishes, obtain midbody 2,5-dioctyl phthalate ethyl ester-3; The ethanolic soln of 4-thiophene two sodium alkoxide, this solution can directly be used for next step reaction, need not any purifying;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic
To in above-mentioned solution, add ethylene dichloride (99g, 1mol), add again the phase-transfer catalyst Tetrabutyl amonium bromide (32.2g, 10%mol); Reflux 4 hours after monitoring reaction finishes, boils off unnecessary ethanol, and oxalic acid diethyl ester; Add ETHYLE ACETATE,, boil off ETHYLE ACETATE, obtain midbody 3 with washing 2 times; 4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene 215g, yield 75%.
Synthesizing of (4) 3,4-enedioxy thiophene (EDOT)
With 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene (209g, (volume ratio is 2:1 0.73mol) to be dissolved in DMSO 99.8MIN. and water; 1.5L) in, (128g 2.19mol), is heated to 120 ℃ of reactions 4 hours to add sodium-chlor; After monitoring reaction finished, rectification under vacuum steamed DMSO 99.8MIN., water, by product ethyl formate and product 3,4-enedioxy thiophene (EDOT); Get EDOT 85g, yield 82%, product E DOT are colourless liquid.
Embodiment 3
(1) the thiodiglycolic acid diethyl ester is synthetic
With ethyl chloroacetate (245.2g, 2.0mol) be added drop-wise to sodium sulphite (78g, in acetone soln 1.0mol) (2L), stirring at room 6 hours generates the thiodiglycolic acid diethyl ester; After monitoring reaction finished, direct filtration, solvent evaporated obtained bullion 324 grams, directly are used for next step reaction, need not to be further purified;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic
Last one the step raw material (324g) is dissolved in (2L) in the ethanol, add under the room temperature in batches sodium ethylate (150g, 2.2mol); Slow adding oxalic acid diethyl ester (146g, 1mol), temperature rising reflux 4 hours; After monitoring reaction finishes, obtain midbody 2,5-dioctyl phthalate ethyl ester-3; The ethanolic soln of 4-thiophene two sodium alkoxide, this solution can directly be used for next step reaction, need not any purifying;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic
To in above-mentioned solution, add ethylene dichloride (148.5g, 1.5mol), add again the phase-transfer catalyst Tetrabutyl amonium bromide (48.3g, 15%mol); Reflux 4 hours after monitoring reaction finishes, boils off unnecessary ethanol, and oxalic acid diethyl ester; Add ETHYLE ACETATE,, boil off ETHYLE ACETATE, obtain midbody 3 with washing 3 times; 4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene 220.4g, yield 77%.
Synthesizing of (4) 3,4-enedioxy thiophene (EDOT)
With 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene (209g, (volume ratio is 4:1 0.73mol) to be dissolved in DMSO 99.8MIN. and water; 1.5L) in, (128g 2.19mol), is heated to 120 ℃ of reactions 4 hours to add sodium-chlor; After monitoring reaction finished, rectification under vacuum steamed DMSO 99.8MIN., water, by product ethyl formate and product 3,4-enedioxy thiophene (EDOT); Get EDOT 86g, yield 83%, product E DOT are colourless liquid.
Embodiment 4
(1) the thiodiglycolic acid diethyl ester is synthetic
With ethyl chloroacetate (245.2g, 2.0mol) be added drop-wise to sodium sulphite (78g, in acetone soln 1.0mol) (2L), stirring at room 6 hours generates the thiodiglycolic acid diethyl ester; After monitoring reaction finished, direct filtration, solvent evaporated obtained bullion 323 grams, directly are used for next step reaction, need not to be further purified;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic
Last one the step raw material (323g) is dissolved in (2L) in the ethanol, add under the room temperature in batches sodium ethylate (150g, 2.2mol); Slow adding oxalic acid diethyl ester (175.2g, 1.2mol), temperature rising reflux 4 hours; After monitoring reaction finishes, obtain midbody 2,5-dioctyl phthalate ethyl ester-3; The ethanolic soln of 4-thiophene two sodium alkoxide, this solution can directly be used for next step reaction, need not any purifying;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic
To in above-mentioned solution, add ethylene dichloride (148.5g, 1.5mol), add again the phase-transfer catalyst Tetrabutyl amonium bromide (64.4g, 20%mol); Reflux 6 hours after monitoring reaction finishes, boils off unnecessary ethanol, and oxalic acid diethyl ester; Add ETHYLE ACETATE,, boil off ETHYLE ACETATE, obtain midbody 3 with washing 4 times; 4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene 229g, yield 80%.
Synthesizing of (4) 3,4-enedioxy thiophene (EDOT)
With 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene (209g, (volume ratio is 4:1 0.73mol) to be dissolved in DMSO 99.8MIN. and water; 1.5L) in, (128g 2.19mol), is heated to 120 ℃ of reactions 4 hours to add sodium-chlor; After monitoring reaction finished, rectification under vacuum steamed DMSO 99.8MIN., water, by product ethyl formate and product 3,4-enedioxy thiophene (EDOT); Get EDOT 86g, yield 83%, product E DOT are colourless liquid.
Embodiment 5
(1) the thiodiglycolic acid diethyl ester is synthetic
With ethyl chloroacetate (245.2g, 2.0mol) be added drop-wise to sodium sulphite (78g, in acetone soln 1.0mol) (2L), stirring at room 6 hours generates the thiodiglycolic acid diethyl ester; After monitoring reaction finished, direct filtration, solvent evaporated obtained bullion 325 grams, directly are used for next step reaction, need not to be further purified;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic
Last one the step raw material (325g) is dissolved in (2L) in the ethanol, add under the room temperature in batches sodium ethylate (150g, 2.2mol); Slow adding oxalic acid diethyl ester (175.2g, 1.2mol), temperature rising reflux 4 hours; After monitoring reaction finishes, obtain midbody 2,5-dioctyl phthalate ethyl ester-3; The ethanolic soln of 4-thiophene two sodium alkoxide, this solution can directly be used for next step reaction, need not any purifying;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic
To in above-mentioned solution, add ethylene dichloride (148.5g, 1.5mol), add again the phase-transfer catalyst Tetrabutyl amonium bromide (64.4g, 20%mol); Reflux 6 hours after monitoring reaction finishes, boils off unnecessary ethanol, and oxalic acid diethyl ester; Add ETHYLE ACETATE,, boil off ETHYLE ACETATE, obtain midbody 3 with washing 3 times; 4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene 229g, yield 80%.
Synthesizing of (4) 3,4-enedioxy thiophene (EDOT)
With 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene (209g, (volume ratio is 4:1 0.73mol) to be dissolved in DMSO 99.8MIN. and water; 1.5L) in, (128g 2.19mol), is heated to 120 ℃ of reactions 6 hours to add sodium-chlor; After monitoring reaction finished, rectification under vacuum steamed DMSO 99.8MIN., water, by product ethyl formate and product 3,4-enedioxy thiophene (EDOT); Get EDOT87g, yield 84%, product E DOT are colourless liquid.
Claims (7)
1. polymer materials monomer 3, the preparation method of 4-enedioxy thiophene comprises:
(1) the thiodiglycolic acid diethyl ester is synthetic:
2:1 is dissolved in ethyl chloroacetate and sodium sulphite in the acetone in molar ratio, stirring at room 2 ~ 6 hours, and reaction finishes after-filtration, and solvent evaporated obtains the thiodiglycolic acid diethyl ester then;
(2) 2,5-dioctyl phthalate ethyl esters-3,4-thiophene two sodium alkoxide synthetic:
Above-mentioned thiodiglycolic acid diethyl ester is dissolved in the ethanol, adds sodium ethylate under the room temperature, slowly add oxalic acid diethyl ester then, reflux obtains midbody 2,5-dioctyl phthalate ethyl ester-3, the ethanolic soln of 4-thiophene two sodium alkoxide after reaction finishes; Wherein the mol ratio of sodium ethylate and ethyl chloroacetate is 2.0 ~ 2.2:1, and the mol ratio of oxalic acid diethyl ester and ethyl chloroacetate is 1.0 ~ 1.2:1;
(3) 3,4-enedioxies-2,5-dioctyl phthalate ethyl ester thiophene synthetic:
At above-mentioned midbody 2,5-dioctyl phthalate ethyl ester-3 adds ethylene dichloride in the ethanolic soln of 4-thiophene two sodium alkoxide; Add phase-transfer catalyst again, reflux 4 ~ 8 hours is after reaction finishes; Boil off unnecessary ethanol and oxalic acid diethyl ester, add ETHYLE ACETATE, boil off ETHYLE ACETATE after the washing; Obtain midbody 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene;
Synthesizing of (4) 3,4-enedioxy thiophene:
With above-mentioned midbody 3,4-enedioxy-2,5-dioctyl phthalate ethyl ester thiophene are dissolved in the mixed solvent of DMSO 99.8MIN. and water composition; Add decarboxylation reagent, be heated to 115-130 ℃ of reaction 2-8 hour then, rectification under vacuum after reaction finishes; Obtain product 3,4-enedioxy thiophene.
2. a kind of polymer materials monomer 3 according to claim 1, the preparation method of 4-enedioxy thiophene is characterized in that: the mol ratio of ethylene dichloride described in the step (3) and ethyl chloroacetate is 1.0 ~ 2.0:1.
3. a kind of polymer materials monomer 3 according to claim 1, the preparation method of 4-enedioxy thiophene is characterized in that: the phase-transfer catalyst described in the step (3) is a Tetrabutyl amonium bromide.
4. according to claim 1 or 3 described a kind of polymer materials monomers 3, the preparation method of 4-enedioxy thiophene is characterized in that: the consumption of the phase-transfer catalyst described in the step (3) is 5 ~ 20% of an ethyl chloroacetate molar weight.
5. a kind of polymer materials monomer 3 according to claim 1, the preparation method of 4-enedioxy thiophene is characterized in that: the volume ratio of DMSO 99.8MIN. and water is 1 ~ 5:1 in the mixed solvent described in the step (4).
6. a kind of polymer materials monomer 3 according to claim 1, the preparation method of 4-enedioxy thiophene is characterized in that: the decarboxylation reagent described in the step (4) is sodium-chlor.
7. according to claim 1 or 6 described a kind of polymer materials monomers 3, the preparation method of 4-enedioxy thiophene is characterized in that: the consumption of the decarboxylation reagent described in the step (4) and the mol ratio of ethyl chloroacetate are 1.2 ~ 3.0:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299463A (en) * | 2018-01-31 | 2018-07-20 | 贝利化学（张家港）有限公司 | A method of preparing two English -2- methanol of thieno [3,4-B] -1,4- |
| CN111100110A (en) * | 2018-10-29 | 2020-05-05 | 浙江京新药业股份有限公司 | Process for preparing 7-piperazinylbenzothiophenes or salts thereof |
| CN115141210A (en) * | 2022-08-06 | 2022-10-04 | 丰宾电子（深圳）有限公司 | Monomer waste liquid recovery treatment method of solid-state aluminum electrolytic capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104619A (en) * | 2007-07-24 | 2008-01-16 | 陕西科技大学 | Decarboxylation preparation technique for ethylene dioxythiophene |
| CN102382122A (en) * | 2011-09-19 | 2012-03-21 | 武汉市祥德科技发展有限公司 | Preparation technology of 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene |
-
2012
- 2012-07-23 CN CN201210254379.XA patent/CN102775423B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104619A (en) * | 2007-07-24 | 2008-01-16 | 陕西科技大学 | Decarboxylation preparation technique for ethylene dioxythiophene |
| CN102382122A (en) * | 2011-09-19 | 2012-03-21 | 武汉市祥德科技发展有限公司 | Preparation technology of 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene |
Non-Patent Citations (2)
| Title |
|---|
| 曾涵等: "3，4-乙撑二氧噻吩合成方法的改进", 《天然产物研究与开发》 * |
| 钱先锋等: "3,4-乙撑二氧噻吩（EDOT）的新合成方法", 《化工新型材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299463A (en) * | 2018-01-31 | 2018-07-20 | 贝利化学（张家港）有限公司 | A method of preparing two English -2- methanol of thieno [3,4-B] -1,4- |
| CN111100110A (en) * | 2018-10-29 | 2020-05-05 | 浙江京新药业股份有限公司 | Process for preparing 7-piperazinylbenzothiophenes or salts thereof |
| CN115141210A (en) * | 2022-08-06 | 2022-10-04 | 丰宾电子（深圳）有限公司 | Monomer waste liquid recovery treatment method of solid-state aluminum electrolytic capacitor |
| CN115141210B (en) * | 2022-08-06 | 2023-09-12 | 丰宾电子科技股份有限公司 | Monomer waste liquid recovery treatment method for solid aluminum electrolytic capacitor |
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