CN102775423B - The preparation method of the ethylenedioxy thiophene of polymeric material monomer 3,4 - Google Patents
The preparation method of the ethylenedioxy thiophene of polymeric material monomer 3,4 Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the ethylenedioxy thiophene of polymeric material monomer 3,4, including：（1）Ethyl chloroacetate and vulcanized sodium are dissolved in acetone, reaction obtains thiodiglycolic acid diethylester；（2）Thiodiglycolic acid diethylester is dissolved in ethanol, caustic alcohol, diethy-aceto oxalate is added, is heated to reflux obtaining the ethanol solution of the sodium alkoxide of 2,53,4 thiophene of dicarboxylic acid ethyl ester two；（3）2, dichloroethanes, TBAB are added in the ethanol solution of the sodium alkoxide of 53,4 thiophene of dicarboxylic acid ethyl ester two, be heated to reflux obtaining the dicarboxylic acid ethyl ester thiophene of 3,4 enedioxy 2,5；（4）By 3, the dicarboxylic acid ethyl ester thiophene of 4 enedioxy 2,5 is dissolved in mixed solvent, adds sodium chloride, heating response, last rectification under vacuum, you can.Preparation method route of the present invention is short, and low cost, process safety reliability, post-processing approach is simple and convenient；The high income of product of the present invention, purity are high.
Description
Technical field
The invention belongs to the preparation field of heterocyclic compound, more particularly to a kind of polymeric material monomer 3,4- enedioxies
The preparation method of thiophene.
Background technology
EDOT is found initially as medicine intermediate, and later its polymer P EODT is again as excellent conductive polymer
Material is found, and so as to start the epoch of macromolecule conducting material, its finder is also awarded Nobel chemistry Prize in 2000.
PEDOT has various advantages such as conductance is high, the good, stability of the transparency is high, easy to process, and for organic thin film solar electricity
Pond material, solid capacitor, electrically conductive ink, OLED material, electrochromic material, antistatic material, Combined Electromagnetic Shielding Materials
Deng multiple fields, and due to its excellent characteristic, PEODT will be used in the research in wider field, and in the market is to the material
The demand of material list body increasingly increases.
3,4- ethylenedioxy thiophenes（EDOT synthesis) just had five classical step synthetic methods of document report early in 1998, but
It is that technique lacks innovation, more falls behind because yield only has 25~30%., Tetrahedron Letters, 45 in 2004
(2004), 6049-6050 reports newest 3,4- ethylenedioxy thiophenes（EDOT) synthetic method, with 2,3- dimethoxy -1,
3- butadiene is exchanged as raw material by cyclization and ether, obtains 3,4-ethylene dioxythiophene（EDOT).But 2,3- dimethoxies
Base -1,3-butadiene market price is expensive, considerably increases the cost of technique, is unfavorable for the control of cost, so this route,
The methodology for being only used for laboratory is explored, and inconvenience is used for industrial production.The Heterocycles of 2010,82 (1), 449-460;
2010 documents, as raw material, by eight one step process, synthesize final products 3,4- ethylenes using butynediols, cylite and bromoethanol
Dioxy thiophene（EDOT), the method used by this article, is suitable only for laboratory method, wherein Lithium Aluminium Hydride and sodium hydrogen, is all
More dangerous industrial chemicals, is not suitable for industrialized production, and using the reaction of eight steps, than classical five-step approach, cause compared with
Cost high, increases the production cycle.The other patent Jpn.Kokai Tokkyo Koho of 2010,2010132571,
17 Jun 2010 be reported in classics five-step approach on change, using methyl chloroacetate and vulcanized sodium as Material synthesis most
Finished product 3,4- ethylenedioxy thiophenes（EDOT), total recovery is 60%, but the temperature control link in the patent is more, is also not suitable for
Technique is amplified.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of system of polymeric material monomer 3,4- ethylenedioxy thiophenes
Preparation Method, the ingenious utilization one kettle way of the method, route is short, with short production cycle, synthesizes low cost, and synthesis technique is safe and reliable, after
Processing method is simple and convenient, and the high income of the product for obtaining, purity is high.
A kind of preparation method of polymeric material monomer 3,4-ethylene dioxythiophene of the invention, including：
（1）The synthesis of thiodiglycolic acid diethylester
In molar ratio 2:1 is dissolved in acetone ethyl chloroacetate and vulcanized sodium, is stirred at room temperature 2 ~ 6 hours, after reaction terminates
Filtering, then solvent evaporated, obtains thiodiglycolic acid diethylester；The thiodiglycolic acid diethylester crude product for obtaining can be directly used for
Next step is reacted, without being further purified；
（2）The synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl ester -3,4- thiophene two
Above-mentioned thiodiglycolic acid diethylester is dissolved in ethanol, caustic alcohol is added at room temperature, be then slowly added into oxalic acid
Diethylester, is heated to reflux, and obtains intermediate 2 after completion of the reaction, 5- dicarboxylic acid ethyl ester -3, the ethanol solution of the sodium alkoxide of 4- thiophene two,
The solution is used directly in next step reaction, without any purifying；Wherein caustic alcohol is with the mol ratio of ethyl chloroacetate
2.0~2.2:1, diethy-aceto oxalate is 1.0 ~ 1.2 with the mol ratio of ethyl chloroacetate:1；
（3）The synthesis of 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
In above-mentioned intermediate 2,5- dicarboxylic acid ethyl ester -3 add dichloroethanes in the ethanol solution of the sodium alkoxide of 4- thiophene two, then
Phase transfer catalyst is added, is heated to reflux 4 ~ 8 hours, after completion of the reaction, boil off unnecessary ethanol and diethy-aceto oxalate, add second
Acetoacetic ester, boils off ethyl acetate after washing, obtain intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene；
（4）3,4- ethylenedioxy thiophenes（EDOT synthesis)
By above-mentioned intermediate 3,4- enedioxies -2,5- dicarboxylic acid ethyl ester thiophene be dissolved in dimethyl sulfoxide (DMSO) and water composition
In mixed solvent, decarboxylation reagent is added, be then heated to 115-130 DEG C and react 2-8 hours, rectification under vacuum after completion of the reaction is obtained
To colorless liquid product 3,4- ethylenedioxy thiophenes（EDOT）.
Step（3）Described in the mol ratio of dichloroethanes and ethyl chloroacetate be 1.0 ~ 2.0:1.
Step（3）Described in phase transfer catalyst be TBAB.
Step（3）Described in phase transfer catalyst consumption for ethyl chloroacetate mole 5 ~ 20%.
Step（4）Described in mixed solvent in the volume ratio of dimethyl sulfoxide (DMSO) and water be 1 ~ 5:1.
Step（4）Described in decarboxylation reagent be sodium chloride.
Step（4）Described in the mol ratio of consumption and ethyl chloroacetate of decarboxylation reagent be 1.2 ~ 3.0:1.
Synthetic route of the invention is as follows：
The sign of sintetics EDOT of the invention：
Below by proton nmr spectra, mass spectrum, compound EDOT of the method such as high resolution gas chromatography to present invention synthesis
Characterized.
1st, hydrogen nuclear magnetic resonance modal data is as follows：
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 chemical shift δ=6.32 (s, 2H) is thiophene fragrance ring hydrogen, 4.19（s,4H）Two between two oxygen atoms
The hydrogen of methylene.
Nuclear magnetic resonance measuring result is defined as 3,4- ethylenedioxy thiophenes（EDOT).
2nd, mass spectrograph determination data is as follows：
ESI-MS(m/z,%)143。
The compound molecular weight is 142, and it is [M+H] to occur 143 in spectrogram+Signal.Mass spectroscopy result is defined as one
Plant novel polymer material monomer 3,4- ethylenedioxy thiophenes（EDOT）.
3rd, high resolution gas chromatography：
Purity is 98 ~ 99%.
The above-mentioned proton nmr spectra of comprehensive analysis, mass spectrum, high resolution gas chromatography shows that the final products that the present invention synthesizes are
3,4- ethylenedioxy thiophenes（EDOT）, and purity is qualified.Its structural formula is：
The total recovery of four-step reaction wherein of the present invention is 57.6 ~ 67.2%.
The present invention is most initial feed with ethyl chloroacetate and vulcanized sodium, by thio, is cyclized and alkylation one kettle way, is taken off
Carboxylic quickly and easily prepare us required for product novel polymer material monomer 3,4- ethylenedioxy thiophenes（EDOT）, and pass through
Liquid chromatogram, nuclear magnetic spectrogram, mass spectrum carry out data characterization.The ingenious utilization one kettle way of present invention process, route is short, the production cycle
It is short, synthesize low cost, synthesis technique is safe and reliable, and post-processing approach is simple and convenient；The high income of product of the present invention（For 57.6 ~
67.2%）, product purity is high（It is 98 ~ 99%）.
Beneficial effect：
1st, the present invention is on the basis of five original classical step synthetic methods, modified technique route, realizes second step and the
The one kettle way of three steps, 72~80% have been brought up to by yield from 40~50%；And last decarboxylation link, also from two original steps
Shorten into a step, not only shorten reaction time, while decreasing the process of post processing, save cost；
2nd, during recovered solvent ethanol and dimethyl sulfoxide (DMSO) can easily cover and use reaction next time in the present invention, reduce
The discharge of toxic reagent and processing cost, meet national green environmental protection and call；
3rd, preparation method of the invention has carried out depth optimization to EDOT existing process, it is possible to achieve extensive to the product
Production, to meet wilderness demand of the domestic and international market to EDOT；
4th, the high income of preparation method of the invention, is 57.6 ~ 67.2%；The purity of the 3,4- ethylenedioxy thiophenes for obtaining
Height, is 98 ~ 99%；And in synthesis and production process, intermediate and final products purity are attained by more than 95%, can meet
Market demands.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
（1）The synthesis of thiodiglycolic acid diethylester
By ethyl chloroacetate（245.2g,2.0mol）It is added drop-wise in the acetone soln of vulcanized sodium (78g, 1.0mol) (2L),
It is stirred at room temperature 2 hours, generates thiodiglycolic acid diethylester；Monitoring after completion of the reaction, is directly filtered, and solvent evaporated obtains crude product
323 grams, next step reaction is directly used in, without being further purified；
（2）The synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl ester -3,4- thiophene two
Previous step raw material（323g）It is dissolved in ethanol（2L）, caustic alcohol is dividedly in some parts at room temperature（136g,2mol）, slowly
Diethy-aceto oxalate (146g, 1mol) is added, temperature rising reflux 4 hours, monitoring after completion of the reaction, obtains intermediate 2,5- dioctyl phthalate second
Ester -3, the ethanol solution of the sodium alkoxide of 4- thiophene two, solution is used directly in next step reaction, without any purifying；
（3）The synthesis of 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
Dichloroethanes will be added in above-mentioned solution（99g,1mol）, add phase transfer catalyst TBAB
(16.1g, 5%mol), is heated to reflux 4 hours, and monitoring after completion of the reaction, boils off unnecessary ethanol, and diethy-aceto oxalate, adds second
Acetoacetic ester, washes with water 3 times, boils off ethyl acetate, obtains intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
211.7g, yield 72%.
（4）3,4- ethylenedioxy thiophenes（EDOT）Synthesis
By 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene（209g,0.73mol）It is dissolved in dimethyl sulfoxide (DMSO) and water
（Volume ratio is 2:1,1.5L）In, add sodium chloride（85.4g,1.46mol）, it is heated to 120 DEG C and reacts 4 hours, monitoring reaction
After finishing, rectification under vacuum steams dimethyl sulfoxide (DMSO), water, byproduct formic acid ethyl ester and product 3,4-ethylene dioxythiophene（EDOT）,
EDOT 83g, yield 80% are obtained, product E DOT is colourless liquid.
Embodiment 2
（1）The synthesis of thiodiglycolic acid diethylester
By ethyl chloroacetate（245.2g,2.0mol）It is added drop-wise in the acetone soln of vulcanized sodium (78g, 1.0mol) (2L),
It is stirred at room temperature 4 hours, generates thiodiglycolic acid diethylester；Monitoring after completion of the reaction, is directly filtered, and solvent evaporated obtains crude product
324 grams, next step reaction is directly used in, without being further purified；
（2）The synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl ester -3,4- thiophene two
Previous step raw material（324g）It is dissolved in ethanol（2L）, caustic alcohol is dividedly in some parts at room temperature（150g,2.2mol）, delay
Slow to add diethy-aceto oxalate (146g, 1mol), temperature rising reflux 4 hours, monitoring after completion of the reaction, obtains intermediate 2,5- dioctyl phthalate
Ethyl ester -3, the ethanol solution of the sodium alkoxide of 4- thiophene two, solution is used directly in next step reaction, without any purifying；
（3）The synthesis of 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
Dichloroethanes will be added in above-mentioned solution（99g,1mol）, add phase transfer catalyst TBAB
(32.2g, 10%mol), is heated to reflux 4 hours, and monitoring after completion of the reaction, boils off unnecessary ethanol, and diethy-aceto oxalate, adds
Ethyl acetate, washes with water 2 times, boils off ethyl acetate, obtains intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
215g, yield 75%.
（4）3,4- ethylenedioxy thiophenes（EDOT synthesis)
By 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene（209g,0.73mol）It is dissolved in dimethyl sulfoxide (DMSO) and water
（Volume ratio is 2:1,1.5L）In, add sodium chloride（128g,2.19mol）, it is heated to 120 DEG C and reacts 4 hours, monitoring has been reacted
Bi Hou, rectification under vacuum steams dimethyl sulfoxide (DMSO), water, byproduct formic acid ethyl ester and product 3,4-ethylene dioxythiophene（EDOT), obtain
EDOT 85g, yield 82%, product E DOT is colourless liquid.
Embodiment 3
（1）The synthesis of thiodiglycolic acid diethylester
By ethyl chloroacetate（245.2g,2.0mol）It is added drop-wise in the acetone soln of vulcanized sodium (78g, 1.0mol) (2L),
It is stirred at room temperature 6 hours, generates thiodiglycolic acid diethylester；Monitoring after completion of the reaction, is directly filtered, and solvent evaporated obtains crude product
324 grams, next step reaction is directly used in, without being further purified；
（2）The synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl ester -3,4- thiophene two
Previous step raw material（324g）It is dissolved in ethanol（2L）, caustic alcohol is dividedly in some parts at room temperature（150g,2.2mol）, delay
Slow to add diethy-aceto oxalate (146g, 1mol), temperature rising reflux 4 hours, monitoring after completion of the reaction, obtains intermediate 2,5- dioctyl phthalate
Ethyl ester -3, the ethanol solution of the sodium alkoxide of 4- thiophene two, solution is used directly in next step reaction, without any purifying；
（3）The synthesis of 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
Dichloroethanes will be added in above-mentioned solution（148.5g,1.5mol）, add phase transfer catalyst tetrabutyl bromine
Change ammonium (48.3g, 15%mol), be heated to reflux 4 hours, monitoring after completion of the reaction, boils off unnecessary ethanol, and diethy-aceto oxalate,
Ethyl acetate is added, is washed with water 3 times, boil off ethyl acetate, obtain intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
220.4g, yield 77%.
（4）3,4- ethylenedioxy thiophenes（EDOT synthesis)
By 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene（209g,0.73mol）It is dissolved in dimethyl sulfoxide (DMSO) and water
（Volume ratio is 4:1,1.5L）In, add sodium chloride（128g,2.19mol）, it is heated to 120 DEG C and reacts 4 hours, monitoring has been reacted
Bi Hou, rectification under vacuum steams dimethyl sulfoxide (DMSO), water, byproduct formic acid ethyl ester and product 3,4-ethylene dioxythiophene（EDOT), obtain
EDOT 86g, yield 83%, product E DOT is colourless liquid.
Embodiment 4
（1）The synthesis of thiodiglycolic acid diethylester
By ethyl chloroacetate（245.2g,2.0mol）It is added drop-wise in the acetone soln of vulcanized sodium (78g, 1.0mol) (2L),
It is stirred at room temperature 6 hours, generates thiodiglycolic acid diethylester；Monitoring after completion of the reaction, is directly filtered, and solvent evaporated obtains crude product
323 grams, next step reaction is directly used in, without being further purified；
（2）The synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl ester -3,4- thiophene two
Previous step raw material（323g）It is dissolved in ethanol（2L）, caustic alcohol is dividedly in some parts at room temperature（150g,2.2mol）, delay
Slow to add diethy-aceto oxalate (175.2g, 1.2mol), temperature rising reflux 4 hours, monitoring after completion of the reaction, obtains intermediate 2,5- bis-
Ethyl formate -3, the ethanol solution of the sodium alkoxide of 4- thiophene two, solution is used directly in next step reaction, without any pure
Change；
（3）The synthesis of 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
Dichloroethanes will be added in above-mentioned solution（148.5g,1.5mol）, add phase transfer catalyst tetrabutyl bromine
Change ammonium (64.4g, 20%mol), be heated to reflux 6 hours, monitoring after completion of the reaction, boils off unnecessary ethanol, and diethy-aceto oxalate,
Ethyl acetate is added, is washed with water 4 times, boil off ethyl acetate, obtain intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
229g, yield 80%.
（4）3,4- ethylenedioxy thiophenes（EDOT synthesis)
By 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene（209g,0.73mol）It is dissolved in dimethyl sulfoxide (DMSO) and water
（Volume ratio is 4:1,1.5L）In, add sodium chloride（128g,2.19mol）, it is heated to 120 DEG C and reacts 4 hours, monitoring has been reacted
Bi Hou, rectification under vacuum steams dimethyl sulfoxide (DMSO), water, byproduct formic acid ethyl ester and product 3,4-ethylene dioxythiophene（EDOT), obtain
EDOT 86g, yield 83%, product E DOT is colourless liquid.
Embodiment 5
（1）The synthesis of thiodiglycolic acid diethylester
By ethyl chloroacetate（245.2g,2.0mol）It is added drop-wise in the acetone soln of vulcanized sodium (78g, 1.0mol) (2L),
It is stirred at room temperature 6 hours, generates thiodiglycolic acid diethylester；Monitoring after completion of the reaction, is directly filtered, and solvent evaporated obtains crude product
325 grams, next step reaction is directly used in, without being further purified；
（2）The synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl ester -3,4- thiophene two
Previous step raw material（325g）It is dissolved in ethanol（2L）, caustic alcohol is dividedly in some parts at room temperature（150g,2.2mol）, delay
Slow to add diethy-aceto oxalate (175.2g, 1.2mol), temperature rising reflux 4 hours, monitoring after completion of the reaction, obtains intermediate 2,5- bis-
Ethyl formate -3, the ethanol solution of the sodium alkoxide of 4- thiophene two, solution is used directly in next step reaction, without any pure
Change；
（3）The synthesis of 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
Dichloroethanes will be added in above-mentioned solution（148.5g,1.5mol）, add phase transfer catalyst tetrabutyl bromine
Change ammonium (64.4g, 20%mol), be heated to reflux 6 hours, monitoring after completion of the reaction, boils off unnecessary ethanol, and diethy-aceto oxalate,
Ethyl acetate is added, is washed with water 3 times, boil off ethyl acetate, obtain intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene
229g, yield 80%.
（4）3,4- ethylenedioxy thiophenes（EDOT synthesis)
By 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene（209g,0.73mol）It is dissolved in dimethyl sulfoxide (DMSO) and water
（Volume ratio is 4:1,1.5L）In, add sodium chloride（128g,2.19mol）, it is heated to 120 DEG C and reacts 6 hours, monitoring has been reacted
Bi Hou, rectification under vacuum steams dimethyl sulfoxide (DMSO), water, byproduct formic acid ethyl ester and product 3,4-ethylene dioxythiophene（EDOT), obtain
EDOT87g, yield 84%, product E DOT is colourless liquid.
Claims (6)
1. a kind of preparation method of polymeric material monomer 3,4-ethylene dioxythiophene, including：
(1) synthesis of thiodiglycolic acid diethylester：
In molar ratio 2:1 is dissolved in acetone ethyl chloroacetate and vulcanized sodium, is stirred at room temperature 2~6 hours, reacts mistake after terminating
Filter, then solvent evaporated, obtains thiodiglycolic acid diethylester；
(2) synthesis of the sodium alkoxide of 2,5- dicarboxylic acid ethyl esters -3,4- thiophene two：
Above-mentioned thiodiglycolic acid diethylester is dissolved in ethanol, caustic alcohol is added at room temperature, be then slowly added into oxalic acid diethyl
Ester, is heated to reflux, and intermediate 2,5- dicarboxylic acid ethyl ester -3, the ethanol solution of the sodium alkoxide of 4- thiophene two are obtained after completion of the reaction；Wherein
Caustic alcohol is 2.0~2.2 with the mol ratio of ethyl chloroacetate:1, the mol ratio of diethy-aceto oxalate and ethyl chloroacetate for 1.0~
1.2:1；
(3) synthesis of 3,4- enedioxies -2,5- dicarboxylic acid ethyl ester thiophene：
In above-mentioned intermediate 2,5- dicarboxylic acid ethyl ester -3 add dichloroethanes, add in the ethanol solution of the sodium alkoxide of 4- thiophene two
Phase transfer catalyst, is heated to reflux 4~8 hours, after completion of the reaction, boils off unnecessary ethanol and diethy-aceto oxalate, adds acetic acid
Ethyl ester, boils off ethyl acetate after washing, obtain intermediate 3,4- enedioxy -2,5- dicarboxylic acid ethyl ester thiophene；
(4) synthesis of 3,4- ethylenedioxy thiophenes：
Above-mentioned intermediate 3,4- enedioxies -2,5- dicarboxylic acid ethyl ester thiophene is dissolved in the mixing of dimethyl sulfoxide (DMSO) and water composition
In solvent, decarboxylation reagent is added, be then heated to 115-130 DEG C and react 2-8 hours, rectification under vacuum after completion of the reaction is produced
Thing 3,4- ethylenedioxy thiophenes；Wherein, decarboxylation reagent is sodium chloride.
2. a kind of preparation method of polymeric material monomer 3,4-ethylene dioxythiophene according to claim 1, its feature
It is：Dichloroethanes and the mol ratio of ethyl chloroacetate described in step (3) are 1.0~2.0:1.
3. a kind of preparation method of polymeric material monomer 3,4-ethylene dioxythiophene according to claim 1, its feature
It is：Phase transfer catalyst described in step (3) is TBAB.
4. the preparation method of a kind of polymeric material monomer 3,4-ethylene dioxythiophene according to claim 1 or 3, it is special
Levy and be：The consumption of the phase transfer catalyst described in step (3) is the 5~20% of ethyl chloroacetate mole.
5. a kind of preparation method of polymeric material monomer 3,4-ethylene dioxythiophene according to claim 1, its feature
It is：Dimethyl sulfoxide (DMSO) and the volume ratio of water are 1~5 in mixed solvent described in step (4):1.
6. a kind of preparation method of polymeric material monomer 3,4-ethylene dioxythiophene according to claim 1, its feature
It is：The consumption of the decarboxylation reagent described in step (4) is 1.2~3.0 with the mol ratio of ethyl chloroacetate:1.
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