CN102633811A - Purification method for preparing high-purity 3,4-ethylenedioxythiophene - Google Patents
Purification method for preparing high-purity 3,4-ethylenedioxythiophene Download PDFInfo
- Publication number
- CN102633811A CN102633811A CN2012101351792A CN201210135179A CN102633811A CN 102633811 A CN102633811 A CN 102633811A CN 2012101351792 A CN2012101351792 A CN 2012101351792A CN 201210135179 A CN201210135179 A CN 201210135179A CN 102633811 A CN102633811 A CN 102633811A
- Authority
- CN
- China
- Prior art keywords
- purity
- product
- enedioxy thiophene
- reaction
- dmf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a purification method for preparing high-purity 3,4-ethylenedioxythiophene. The steps are as follows: in a 1000mL three-neck flask, 100g of 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid is dissolved in 500mL of DMF (dimethyl formamide), 6g of catalyst is added, the temperature is increased to 150 DEG C, and reaction is carried out for 5 to 7 hours; when no materials are detected by thin-Layer chromatography, heating is stopped, and the DMF is distilled off under reduced pressure, so that crude product is obtained; 600mL of water is added into the reaction system, steam distillation is carried out, and when distilled water is clear, distillation is finished; dichloromethane is used for extraction for three times, extracts are combined, dried and concentrated, so that colorless or pale yellow oily liquid is obtained, and after reduced pressure distillation, colorless product is obtained; the product yield is calculated, and the purity of the product is calculated by HPLC (high performance liquid chromatography) detection. The EDOT (3,4-ethylenedioxythiophene) product, the purity of which is greater than 99.9 percent and which can meet the requirement of electronic chemicals, can be obtained by the purification method, moreover, the last step of postprocessing is simple, and the purification method is easy to operate, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind ofly 3, the purification process of 4-enedioxy thiophene specially refers to a kind of preparation high purity 3, the purification process of 4-enedioxy thiophene.
Background technology
Gather enedioxy thiophene (be called for short PEDOT) and be a kind of novel organic conductive luminescent material that German Bayer company develops, advantage such as have that electric conductivity height, environmental stability are good, film is prone to system and the transparency is good.The main application of PEDOT comprises: (1) application in solid electrolyte capacitators; (2) application in antistatic coating; (3) application in photovoltaic cell; (4) application in organic electroluminescence device.In addition, PEDOT also has broad application prospects at aspects such as transmitter, rechargeable battery, corrosion protections.Therefore, gather the focus that enedioxy thiophene (PEDOT) has become conductive polymers research.The synthetic of PEDOT is that monomer whose EDOT obtains through chemical polymerization or electrochemical polymerization; And the purposes of the EDOT synthetic PEDOT of different purity is also different, and high purity EDOT synthetic PEDOT has very superior performance when being applied to fields such as solid electrolyte as macromolecular material.So preparing the highly purified EDOT that meets the electronic chemical product requirement has very important significance.
About the preparation of monomer EDOT, existing both at home and abroad many pieces of bibliographical informations, but main compound method has two kinds; A kind of method is Jonas (Jonas; F. EP:440957,1990) " five-step approach " of the classics of invention, this method are to be raw material with sulfo-two sweet acid; Synthesize 3,4-enedioxy thiophene through esterification, condensation, cyclic ethersization, hydrolysis, decarboxylation five steps reaction.Synthetic route is following:
Along with the application of PEDOT more and more widely, people are also heated up for the research of EDOT gradually, many synthetic work persons improve on " five-step approach " basis of classics, have worked out other compound method.Appoint the spring and (CN101062927) above-mentioned compound method is improved, pass through to add phase-transfer catalyst, the yield of this step reaction is significantly improved in the process of the 3rd step cyclic ethersization.And making the reaction of nine hydrated sodium sulfides and ethyl chloroacetate into, Chen Yuanwei (CN 101519409A) the first step esterification that yield is lower synthesizes sulfo-two sweet diethyl phthalates; Adopt cheap ethyl chloroacetate to react and be more suitable for suitability for industrialized production, synthetic route is following:
The purity of the finished product and the post-treating method of final step are closely related; When producing according to the post-treating method of above bibliographical information, operate more loaded down with trivial details, relate to pickling, rectification under vacuum etc. a series of to equipment requirements than higher operation; The most important is according to the aforesaid operations method; The purity of the finished product EDOT is not easy to reach the requirement of electronic chemical product, exists product colour to lay particular stress on, the shortcoming that single foreign matter content is higher.
A kind of in addition synthetic route is to be raw material with thiophene and liquid bromine, and is synthetic 3 through bromo, reduction, alkoxylate and ether exchange four-step reaction, 4-enedioxy thiophene.Concrete synthetic route is (CN 101220038A) as follows:
Through consulting document and experiment being verified; Find that above two kinds of synthetic routes all are difficult to obtain purity and meet 3 of electronic chemical product requirement, 4-enedioxy thiophene is for first kind of synthetic route; Last handling processes such as the pickling that the aftertreatment of final step decarboxylation relates to, washing, extraction; Operate more loaded down with trivial detailsly, and be not easy to obtain purity and meet 3 of electronic chemical product requirement, 4-enedioxy thiophene.For second kind of synthetic route, Chinese patent CN 101220038A reported method, final product 3, the purity of 4-enedioxy thiophene also is difficult to reach the requirement of electronic chemical product.
Summary of the invention
The invention reside in provides a kind of preparation high purity 3, the purification process of 4-enedioxy thiophene, and purpose is to be intended to overcome 3, and 4-enedioxy thiophene compound purity is lower, can not meet the deficiency of electronic chemical product demand.
For realizing above-mentioned technical purpose, solve the deficiency of prior art, the present invention realizes through following technical scheme:
A kind of preparation high purity 3, the purification process of 4-enedioxy thiophene may further comprise the steps:
Step 1) is in the there-necked flask of 1000mL, and with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, adds 200-300 order copper powder 6g, is warming up to 150
oC, reaction in 5-7 hour is accomplished;
Step 2) TLC detects no raw material, stops heating, removes DMF under reduced pressure, obtains the bullion product;
Step 3) adds 600mL water then in reaction system, carry out wet distillation, when seeing that the clarification of water that distills shows the distillation completion when transparent;
Step 4) is with dichloromethane extraction three times, combining extraction liquid, and dry concentrating obtains colourlessly to light yellow oily liquid, and underpressure distillation obtains colorless product;
Step 5) counting yield yield detects counting yield purity through HPLC.
Further, in the said step 1), said catalyzer is a 200-300 order copper powder.
Further, in the said step 1), said catalyzer is a ventilation breather.
Further, said step 1), in the there-necked flask of 1000mL, with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, add 200-300 order copper powder 6g, are warming up to 150
oC continues bubbling air during reaction, reaction is accomplished about 5-7 hour.
Further, said step 1), in the there-necked flask of 1000mL, with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, add 200-300 order copper powder 6g, are warming up to 150
oC, the inflated with nitrogen protection, reaction is accomplished about 5-7 hour.
Compared with prior art, the present invention has following beneficial effect:
Maximum characteristics of the present invention are can obtain purity greater than 99.9% the EDOT product that electronic chemical product requires that meets, and the aftertreatment of final step is simple, and easy handling is fit to suitability for industrialized production.
After this decarboxylic reaction finishes, adopt steam distillation to carry out aftertreatment and can obtain purity, and operation is easier, is easy to suitability for industrialized production greater than 99.9% product.
Also changed different catalyst simultaneously and reaction conditions makes an experiment; The final product gas purity of finding all can reach the requirement of electronic chemical product; This shows the purpose that adopts steam distillation can be issued to purified product in multiple various conditions, shows that this method has excellent adaptability.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention, understands technological technical scheme of the present invention in order can more to know, and can implement according to the content of specification sheets, below with preferred embodiment of the present invention.
Embodiment
Embodiment 1
In the there-necked flask of 1000mL, with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, add 200-300 order copper powder 6g, are warming up to 150
oC continues bubbling air during reaction, reaction is accomplished about 6 hours.TLC detects no raw material, stops heating, removes DMF under reduced pressure, obtains the bullion product; In reaction system, add 600mL water then, carry out wet distillation, when seeing that the clarification of water that distills shows when transparent that distillation accomplishes, with dichloromethane extraction three times; Combining extraction liquid, drying concentrates and obtains colourless extremely light yellow oily liquid, and underpressure distillation obtains colorless product 40.2g; Yield 63.3% detects product purity through HPLC>99.9%.
Embodiment 2
In the there-necked flask of 1000mL, with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, add 200-300 order copper powder 6g, are warming up to 150
oC, nitrogen protection, reaction is accomplished about 5 hours.TLC detects no raw material, stops heating, removes DMF under reduced pressure, obtains the bullion product; In reaction system, add 600mL water then, carry out wet distillation, when seeing that the clarification of water that distills shows when transparent that distillation accomplishes, with dichloromethane extraction three times; Combining extraction liquid, drying concentrates and obtains colourless extremely light yellow oily liquid, and underpressure distillation obtains colorless product 42.1g; Yield 66.3% detects product purity through HPLC>99.9%.
Embodiment 3
In the there-necked flask of 1000mL, with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, add ventilation breather 6g, are warming up to 150
oC, reaction is accomplished about 7 hours.TLC detects no raw material, stops heating, removes DMF under reduced pressure, obtains the bullion product; In reaction system, add 600mL water then, carry out wet distillation, when seeing that the clarification of water that distills shows when transparent that distillation accomplishes, with dichloromethane extraction three times; Combining extraction liquid, dry concentrating obtains colourless extremely light yellow oily liquid, and underpressure distillation obtains colorless product 45.3g; Yield 71.3% detects product purity through HPLC>99.9%.
Embodiment 4
In the there-necked flask of 1000mL, with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, add 400 order copper powder 6g, are warming up to 150
oC, reaction is accomplished about 5 hours.TLC detects no raw material, stops heating, removes DMF under reduced pressure, obtains the bullion product; In reaction system, add 600mL water then, carry out wet distillation, when seeing that the clarification of water that distills shows when transparent that distillation accomplishes, with dichloromethane extraction three times; Combining extraction liquid, drying concentrates and obtains colourless extremely light yellow oily liquid, and underpressure distillation obtains colorless product 48.6g; Yield 76.5% detects product purity through HPLC>99.9%.
The above is merely preferred case study on implementation of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. one kind prepares high purity 3, and the purification process of 4-enedioxy thiophene is characterized in that, may further comprise the steps:
Step 1) is in the there-necked flask of 1000mL, and with 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF, adds catalyzer 6g, is warming up to 150
oC, reaction in 5-7 hour is accomplished;
Step 2) TLC detects no raw material, stops heating, removes DMF under reduced pressure, obtains the bullion product;
Step 3) adds 600mL water then in reaction system, carry out wet distillation, when seeing that the clarification of water that distills shows the distillation completion when transparent;
Step 4) is with dichloromethane extraction three times, combining extraction liquid, and dry concentrating obtains colourlessly to light yellow oily liquid, and underpressure distillation obtains colorless product;
Step 5) counting yield yield detects counting yield purity through HPLC.
2. preparation high purity 3 according to claim 1, the purification process of 4-enedioxy thiophene is characterized in that: in the said step 1), said catalyzer is a 200-400 order copper powder.
3. preparation high purity 3 according to claim 1, the purification process of 4-enedioxy thiophene is characterized in that: in the said step 1), said catalyzer is copper powder or ventilation breather.
4. according to claim 1 or 2 or 3 described preparation high purities 3, the purification process of 4-enedioxy thiophene is characterized in that: in the said step 1); In the there-necked flask of 1000mL; With 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF; Add catalyzer, be warming up to 150
oC continues bubbling air during reaction, reaction is accomplished about 5-7 hour.
5. according to claim 1 or 2 or 3 described preparation high purities 3, the purification process of 4-enedioxy thiophene is characterized in that: in the said step 1); In the there-necked flask of 1000mL; With 100g 3,4-enedioxy thiophene-2,5-dicarboxylicacid are dissolved among the 500 mL DMF; Add catalyzer, be warming up to 150
oC, the inflated with nitrogen protection, reaction is accomplished about 5-7 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101351792A CN102633811A (en) | 2012-05-04 | 2012-05-04 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101351792A CN102633811A (en) | 2012-05-04 | 2012-05-04 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102633811A true CN102633811A (en) | 2012-08-15 |
Family
ID=46618404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101351792A Pending CN102633811A (en) | 2012-05-04 | 2012-05-04 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633811A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519409A (en) * | 2008-02-27 | 2009-09-02 | 成都丽凯手性技术有限公司 | Method for preparing 3, 4-ethylenedioxythiophene |
| JP2010095469A (en) * | 2008-10-16 | 2010-04-30 | Tama Kagaku Kogyo Kk | Method for producing 3,4-dialkoxy (or alkylenedioxy) thiophene |
| CN102241691A (en) * | 2011-07-13 | 2011-11-16 | 西北大学 | Decarboxylation method of 3,4-ethylenedioxy thiophene |
-
2012
- 2012-05-04 CN CN2012101351792A patent/CN102633811A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519409A (en) * | 2008-02-27 | 2009-09-02 | 成都丽凯手性技术有限公司 | Method for preparing 3, 4-ethylenedioxythiophene |
| JP2010095469A (en) * | 2008-10-16 | 2010-04-30 | Tama Kagaku Kogyo Kk | Method for producing 3,4-dialkoxy (or alkylenedioxy) thiophene |
| CN102241691A (en) * | 2011-07-13 | 2011-11-16 | 西北大学 | Decarboxylation method of 3,4-ethylenedioxy thiophene |
Non-Patent Citations (1)
| Title |
|---|
| 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》, vol. 35, no. 2, 28 February 2007 (2007-02-28), pages 1 - 5 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101062927B (en) | Preparation method of 3,4-ethene dioxythiophene | |
| CN105218558B (en) | A kind of benzene thiophene class organic photoelectric compound and its preparation method and application | |
| CN101220038A (en) | 3,4-ethylene dioxythiophene synthesizing method | |
| US8735605B2 (en) | Heterocyclic quinoid thiophene organic photoelectric material, preparation method and application thereof | |
| CN105622442A (en) | Tert-butyl spirobifluorene compound and preparation method and application thereof | |
| CN110229315A (en) | A kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide | |
| CN109912621B (en) | Asymmetric naphthalene nucleus small molecule receptor material and preparation method and application thereof | |
| CN110105375A (en) | Give-by-to type Uniformpoly thiophene derivative and preparation method thereof to-by-using dithieno pyrroles as molecular center | |
| CN102633811A (en) | Purification method for preparing high-purity 3,4-ethylenedioxythiophene | |
| CN103951813B (en) | 9-aryl replaces fluorenyl conjugated polyelectrolytes and its preparation method and application | |
| CN102887868A (en) | Preparation method of triallyl isocyanurate | |
| US20120241004A1 (en) | Thiophene-containing organic photoelectric materials, their preparation methods and solar cell devices | |
| CN102952004B (en) | Technology for separating ethylene glycol monomethyl ether and water by use of continuous azeotropic distillation method | |
| CN102532492A (en) | Crosslinking thiopheno[3,4-b] thiophene conjugated polymer and preparation method and application thereof | |
| CN108409755A (en) | A kind of organic photoelectric conversion material, preparation method and application | |
| CN114479019B (en) | Triazine polymer material, preparation method thereof and application thereof in photoelectric device | |
| CN105936620A (en) | Ethylene glycol purifying apparatus in environmentally-friendly plasticizer DOTP preparation process, and purifying technology thereof | |
| CN108117498B (en) | Synthesis method of gemini surfactant | |
| CN101591345B (en) | Synthesizing method of conductive high polymer monomer | |
| CN102002057A (en) | Preparation method for 3,4-ethylene dioxythiophene-2,5-dicarboxylic acid dimethyl ester | |
| CN103554517B (en) | A kind of new and effective PPV base organic photovoltaic material and preparation method thereof | |
| CN104250364B (en) | A kind of amphion amido polyfluorene derivative and its synthetic method and application | |
| CN102381971A (en) | Preparation method of light stabilizer intermediate acrylic acid (2'-chloroethyl) ester | |
| CN107629067B (en) | A kind of dithieno cyclopentadiene derivant and preparation method thereof | |
| CN102079748B (en) | Synthesis method of 3,4-ethylenedioxythiophene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120815 |