CN102477044A - Synthetic method of monomer 3,4-ethylenedioxythiophene (EDOT) of conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) - Google Patents
Synthetic method of monomer 3,4-ethylenedioxythiophene (EDOT) of conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) Download PDFInfo
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- CN102477044A CN102477044A CN2010105619541A CN201010561954A CN102477044A CN 102477044 A CN102477044 A CN 102477044A CN 2010105619541 A CN2010105619541 A CN 2010105619541A CN 201010561954 A CN201010561954 A CN 201010561954A CN 102477044 A CN102477044 A CN 102477044A
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Abstract
The invention discloses a synthetic method of monomer 3,4-ethylenedioxythiophene (EDOT) of a conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). The method has the advantages of convenient obtainment of raw materials used herein, low price, and low cost of production materials. Compared with the prior art, a decarboxylation reaction adopts an ionic liquid as a solvent, and the method is novel and is suitable for industrial production. The method adopts the ionic liquid and copper oxide as catalysts, thus the system can be repeatedly used, and the production cost can be reduced.
Description
Technical field
The present invention relates to a kind of conducting polymer and gather 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), 4-ethene dioxythiophene (EDOT) synthetic.
Background technology
3,4-ethene dioxythiophene (EDOT), outward appearance is colourless or light yellow transparent liquid, CAS:126213-50-1,10.5 ℃ of fusing points, 225 ℃ of boiling points (101.3kpa).Its main application is to be used to prepare conducting polymer to gather 3 4-ethene dioxythiophene (PEDOT).Gather 3,4-ethene dioxythiophene (PEDOT) is a kind of novel organic conductive luminescent material, has the following advantages: (1) electric conductivity high (its least surface resistance can reach 200 Ω/cm 3); (2) transparency is good; (3) thermostability, light stability and the resistance to hydrolysis of excellence; (4) handling ease; It is the ideal material of electronicss such as the demonstration of preparation organic electroluminescence, solar cell, ultracapacitor plastics antistatic coating, illumination film coating, transmitter, corrosion protection; Therefore in various fields purposes is widely arranged all, because its unique electricity and optical characteristics, the market requirement increases year by year; Therefore study monomer 3, the preparation of 4-ethene dioxythiophene (EDOT) seems particularly important.
About monomer 3, the preparation of 4-ethene dioxythiophene (EDOT), existing many reports in the document.The required solvent of final step decarboxylic reaction bibliographical information is YLENE, quinoline, Witcizer 300, polyoxyethylene glycol etc.; The present invention adopts ionic liquid to make the decarboxylation solvent; Having obtained comparatively desired result equally, is a kind of comparatively green synthetic 3, the method for 4-ethene dioxythiophene (EDOT); And ionic liquid can reuse more than 5 times, and productive rate is not seen obvious decline.
When comparing with ionogen with conventional organic solvents, ionic liquid has a series of outstanding advantages: (1) liquid wide ranges, from being lower than or, high thermostability and chemicalstability being arranged near more than the room temperature to 300 degree centigrade; (2) vp is very little, and is non-volatile, in using, storing, can not evaporate lost; Can recycle; Eliminated volatile organic compounds (VOCs, i.e. volative organic compounds) problem of environmental pollution, (3) specific conductivity is high; Electrochemical window is big, can be used as the electrolytic solution of many material electrochemical researchs; (4) its solvability of design adjustable through zwitterion to inorganics, water, organism and polymkeric substance, and its acidity can transfer to super acid.(4) have bigger polarity Modulatory character, viscosity is low, and density is big, can form two-phase or heterogeneous system, is fit to make to separate solvent or constitute reaction-separation coupling new system; (5) to a large amount of inorganic and organic substances performance place good dissolving ability all, and have the dual-use function of solvent and catalyzer, can be used as many chemical reaction solvents or catalytic activity carrier.Because ion liquid these special propertys and performance, it is considered to and supercritical CO 2 and double water-phase constitute three big green solvents together, has broad application prospects.
Ion liquid synthetic
X is Cl, Br, I, PF in the formula
6And BF
4In any one.
Summary of the invention
For addressing the above problem; The objective of the invention is to overcome above-mentioned deficiency; Provide a kind of conducting polymer to gather 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), the compound method of 4-ethene dioxythiophene (EDOT); Have that raw material is easy to get, cost is lower, yield is higher, simple to operate, green advantage such as synthetic, be suitable for need of industrial production.
For achieving the above object, technical scheme of the present invention is: a kind of conducting polymer gathers 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), and the compound method of 4-ethene dioxythiophene (EDOT), said 3, the 4-ethene dioxythiophene has structure shown in the formula (1):
It is characterized in that its compound method may further comprise the steps:
Step 1 is carried out condensation reaction with sulfo-two sweet dimethyl phthalates and oxalic acid diethyl ester under sodium methylate/methyl alcohol condition, reaction finishes back acidifying, filtration, drying, obtains 2 of structure shown in the formula (2), 5-dioctyl phthalate dimethyl ester-3, and 4-dihydroxyl thiophene:
Step 2, with obtain in the step 12,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene with
1, the 2-ethylene dichloride, salt of wormwood, phase-transfer catalyst reacts in suitable solvent, after reaction 5 finishes, reclaims solvent, adds water after the cooling, suction filtration, washing, drying obtains formula (3)
Shown in the etherificate product 2 of structure, 5-dioctyl phthalate dimethyl ester-3, the 4-ethene dioxythiophene:
Step 3, with obtain in the step 22,5-dioctyl phthalate dimethyl ester-3, the reaction of 4-ethene dioxythiophene and aqueous sodium hydroxide solution, after reaction finishes, acidifying, suction filtration, washing, drying obtains 2 of structure shown in the formula (4), 5-dioctyl phthalate-3, the 4-ethene dioxythiophene:
Step 4, with obtain in the step 32,5-dioctyl phthalate-3; The 4-ethene dioxythiophene is made reaction solvent with ionic liquid under suitable temperature and catalyzer, and nitrogen protection is reaction down; Reaction finishes postcooling, and solution carries out underpressure distillation and obtains 3 of structure shown in the formula (1), 4-ethene dioxythiophene.
Preferably, said step 1 to the reaction formula of step 4 is:
Preferably, the mol ratio of the two sweet dimethyl phthalates of the sulfo-described in the step 1, sodium methylate, oxalic acid diethyl ester is 1: 3-10: 1-5; The concentration of described sodium methylate/methanol solution is 18.8%.
Preferably; Described in the step 22; 5-dioctyl phthalate dimethyl ester-3; 4-dihydroxyl thiophene, 1, the mol ratio of 2-ethylene dichloride, salt of wormwood are 1: 1-8: 1-5, described phase-transfer catalyst are Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, CETRIMIDE POWDER or tetrabutylammonium iodide.
Preferably, 2 described in the step 3,5-dioctyl phthalate dimethyl ester-3, the mol ratio of 4-ethene dioxythiophene and sodium hydroxide is 1: 3-1: 8.
Preferably, the suitable temperature described in the step 4 is 80 ℃-180 ℃; Described catalyzer is cupric oxide, copper powder, verditer or verditer; Described ionic liquid is:
Preferably, the concentration of the sodium methylate/methanol solution described in the step 1 is 18.8%.
Adopt the beneficial effect of present technique scheme to be: raw material sources used in the present invention are convenient, and cheap, the production material cost is lower.The present invention compared with prior art, decarboxylic reaction adopts ionic liquid to make solvent, method is novel, is suitable for suitability for industrialized production.The present invention uses ionic liquid and copper oxide catalyst, and system can be reused, and has reduced production cost.
Embodiment
With regard to embodiment the present invention is done further detailed explanation below.
Embodiment 1,
Step 1: 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene synthetic.
In the three-necked flask of a 5L, add (380g, 2.13mol) sulfo-two sweet dimethyl phthalates and (460g, 8.52mol) the 2.5L methanol solution of sodium methylate, controlled temperature 0-10 ℃; (772g, 5.33mol) oxalic acid diethyl ester dropwise back back flow reaction 6h, react the back that finishes and concentrate to stir adding down; Add water 1L, use hcl acidifying, filter, drying obtains off-white color pressed powder 2; 5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene 460g, content 99.1%, productive rate 92%.
Step 2: 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene synthetic.
In the reaction kettle of a 10L, add (440g, 1.9mol) 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene; (632g, 6.38mol) 1,2-ethylene dichloride, (504g, 3.65mol) salt of wormwood; 25g Tetrabutyl amonium bromide (phase-transfer catalyst) and 5LDMF stir and to be warming up to about 90 ℃, reaction 12h, and reaction finishes the back concentrating under reduced pressure and reclaims solvent and unreacted 1,2-ethylene dichloride; The cooling back adds 1.5L water, stirring at room 1h, and suction filtration is washed successively, and drying obtains off-white color to pale solid powder 2; 5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene 330g, content 98.2%, productive rate 65%.
Step 3: 2,5-dioctyl phthalate-3,4-ethene dioxythiophene synthetic.
In the three-necked flask of a 5L, add (310g, 1.18mol) 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene; (2L water mixes stirring for 200g, sodium hydroxide 5mol), and temperature rising reflux 3h reduces to room temperature hydrochloric acid after reaction finishes and is acidified to PH=1-2; Separate out pale precipitation, suction filtration, the less water washing obtains pale solid powder 2 after the drying; 5-dioctyl phthalate-3,4-ethene dioxythiophene 260g, content 99.2%, productive rate 95%.
Step 4: 3,4-ethene dioxythiophene synthetic.
In the three-necked flask of a 5L, add (255g, 1.1mol) 2,5-dicarboxylic acid esters-3, the 4-ethene dioxythiophene, 100g verditer (catalyzer), 2L iodate 1-methyl-3-n-hexyl imidazoles (solvent) is warming up to 180 ℃, reaction 18h.Reaction is reduced to room temperature after finishing, and solution carries out underpressure distillation and obtains 3,4-ethene dioxythiophene 140g, content 99.2%, productive rate 90%.
Embodiment 2,
All the other steps are identical with embodiment 1, and difference is, step 4: 3, and 4-ethene dioxythiophene synthetic.
In the three-necked flask of a 5L, add (255g, 1.1mol) 2,5-dicarboxylic acid esters-3, the 4-ethene dioxythiophene, 80g cupric oxide (catalyzer), 2L iodate 1-methyl-3-n-hexyl imidazoles (solvent) is warming up to 180 ℃, reaction 18h.Reaction is reduced to room temperature after finishing, and solution carries out underpressure distillation and obtains 3,4-ethene dioxythiophene 135g, content 99.2%, productive rate 88%.
Embodiment 3,
All the other steps are identical with embodiment 1, and difference is, step 4: 3, and 4-ethene dioxythiophene synthetic.
In the three-necked flask of a 5L, add (255g, 1.1mol) 2,5-dicarboxylic acid esters-3, the 4-ethene dioxythiophene, 80g cupric oxide (catalyzer), 2L bromination 1-methyl-3-n-hexyl imidazoles (solvent) is warming up to 180 ℃, reaction 18h.Reaction is reduced to room temperature after finishing, and solution carries out underpressure distillation and obtains 3,4-ethene dioxythiophene 136g, content 99.2%, productive rate 88%.
With bromination 1-methyl-3-n-hexyl imidazoles is solvent, cupric oxide be catalyzer repeat make 5 to use situation:
| Number of times | Productive rate | Content |
| 1 | 88％ | 99.2％ |
| 2 | 86.5％ | 99.2％ |
| 3 | 86％ | 99.1％ |
| 4 | 85％ | 99.1％ |
| 5 | 80％ | 99.0％ |
In the foregoing description, sodium methylate/methanol concentration is 18.8%.
Adopt the beneficial effect of present technique scheme to be: raw material sources used in the present invention are convenient, and cheap, the production material cost is lower.The present invention compared with prior art, decarboxylic reaction adopts ionic liquid to make solvent, method is novel, is suitable for suitability for industrialized production.The present invention uses ionic liquid and copper oxide catalyst, and system can be reused, and has reduced production cost.
Above-described only is preferred implementation of the present invention, should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (7)
1. a conducting polymer gathers 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), and the compound method of 4-ethene dioxythiophene (EDOT), said 3, the 4-ethene dioxythiophene has structure shown in the formula (1):
It is characterized in that its compound method may further comprise the steps:
Step 1 is carried out condensation reaction with sulfo-two sweet dimethyl phthalates and oxalic acid diethyl ester under sodium methylate/methyl alcohol condition, reaction finishes back acidifying, filtration, drying, obtains 2 of structure shown in the formula (2), 5-dioctyl phthalate dimethyl ester-3, and 4-dihydroxyl thiophene:
Step 2, with obtain in the step 12,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene and 1; The 2-ethylene dichloride, salt of wormwood, phase-transfer catalyst reacts in suitable solvent, after reaction finishes; Reclaim solvent, add water after the cooling, suction filtration, washing; Drying obtains the etherificate product 2 of structure shown in the formula (3), 5-dioctyl phthalate dimethyl ester-3, and the 4-ethene dioxythiophene:
Step 3, with obtain in the step 22,5-dioctyl phthalate dimethyl ester-3, the reaction of 4-ethene dioxythiophene and aqueous sodium hydroxide solution, after reaction finishes, acidifying, suction filtration, washing, drying obtains 2 of structure shown in the formula (4), 5-dioctyl phthalate-3, the 4-ethene dioxythiophene:
Step 4, with obtain in the step 32,5-dioctyl phthalate-3; The 4-ethene dioxythiophene is made reaction solvent with ionic liquid under suitable temperature and catalyzer, and nitrogen protection is reaction down; Reaction finishes postcooling, and solution carries out underpressure distillation and obtains 3 of structure shown in the formula (1), 4-ethene dioxythiophene.
2. conducting polymer according to claim 1 gathers 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), and the compound method of 4-ethene dioxythiophene (EDOT) is characterized in that, said step 1 to the reaction formula of step 4 is:
3. conducting polymer according to claim 1 gathers 3; The monomer 3 of 4-ethene dioxythiophene (PEDOT); The compound method of 4-ethene dioxythiophene (EDOT); It is characterized in that the mol ratio of the sulfo-two sweet dimethyl phthalates described in the step 1, sodium methylate, oxalic acid diethyl ester is 1: 3-10: 1-5; The concentration of described sodium methylate/methanol solution is 18.8%.
4. conducting polymer according to claim 1 gathers 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), the compound method of 4-ethene dioxythiophene (EDOT); It is characterized in that; Described in the step 22,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene, 1; The mol ratio of 2-ethylene dichloride, salt of wormwood is 1: 1-8: 1-5, described phase-transfer catalyst are Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, CETRIMIDE POWDER or tetrabutylammonium iodide.
5. conducting polymer according to claim 1 gathers 3; The monomer 3 of 4-ethene dioxythiophene (PEDOT); The compound method of 4-ethene dioxythiophene (EDOT) is characterized in that, 2 described in the step 3; 5-dioctyl phthalate dimethyl ester-3, the mol ratio of 4-ethene dioxythiophene and sodium hydroxide are 1: 3-1: 8.
6. conducting polymer according to claim 1 gathers 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), and the compound method of 4-ethene dioxythiophene (EDOT) is characterized in that, the suitable temperature described in the step 4 is 80 ℃-180 ℃; Described catalyzer is cupric oxide, copper powder, verditer or verditer; Described ionic liquid is:
7. conducting polymer according to claim 3 gathers 3, the monomer 3 of 4-ethene dioxythiophene (PEDOT), and the compound method of 4-ethene dioxythiophene (EDOT) is characterized in that, the concentration of the sodium methylate/methanol solution described in the step 1 is 18.8%.
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| CN104016999A (en) * | 2014-06-27 | 2014-09-03 | 江西科技师范大学 | Method for preparing 3,4-alkylenedioxyfuran compound |
| CN109382139A (en) * | 2017-08-07 | 2019-02-26 | 南京宜凯瑞新材料有限公司 | It is used to prepare the new catalyst of 3,4- propylene dioxy thiophene and its derivative |
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| CN109382139A (en) * | 2017-08-07 | 2019-02-26 | 南京宜凯瑞新材料有限公司 | It is used to prepare the new catalyst of 3,4- propylene dioxy thiophene and its derivative |
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