CN1616454A - Preparation of thiophene monomer and its polymerizing method - Google Patents
Preparation of thiophene monomer and its polymerizing method Download PDFInfo
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- CN1616454A CN1616454A CN 200410066866 CN200410066866A CN1616454A CN 1616454 A CN1616454 A CN 1616454A CN 200410066866 CN200410066866 CN 200410066866 CN 200410066866 A CN200410066866 A CN 200410066866A CN 1616454 A CN1616454 A CN 1616454A
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Abstract
The present invention belongs to the field of fine chemical technology, and relates to especially the preparation and application of thiophene monomer for polymer. The present invention provides one process of preparing high purity thiophene monomer and its polymer in high yield and the application of thiophene polymer. Polythiophene and its derivatives are applied increasingly in transparent conducting film for display screen. The present invention provides thiophene preparing process with simple purification, high stability of polymer system and high transparency and conductivity of the polymer film, and may be used widely in the production of transmission layer material for circuit board and electroluminescent display device.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to a kind of preparation and application of thiophene monomer.The invention provides and a kind ofly prepare the method for high-purity, high yield thiophene monomer with rough thiophene monomer, and the application aspect the preparation thiofuran polymer.
Background technology
Transparent conductive film is used for the transparency electrode of coating of liquid crystalline display screen, electroluminescent display panel, plasma display panel (PDP), electrochromism display screen, solar cell, touch-screen etc.Kind electrode generally is the indium-tin oxide electrode (being the ITO electrode) that adopts the method acquisition of vapor deposition.But the cost height, make that the influence factor of electroconductibility of complicated, film is many etc. to make people seek its substitute.Simultaneously raising and the science and technology along with people's daily life level is constantly progressive, becomes a kind of trend and fashion based on the display screen of flexible parent metal (carrier of conductive film).And the conductivity of ITO conductive film on flexible parent metal descends and comes off, and can not satisfy people's demand.The snappiness of conductive conjugated polymer and wide conductive characteristic (can be the conductive characteristic of semi-conductive characteristic and metal) and caused that people note widely.In conductive conjugated polymer research, Polythiophene and derivative thereof become the bright spot in the research, and poly-dialkoxythiophene and polyalkylene dioxy thiophene form and are the most important thing because of self stability and conductive characteristic.
Poly-dialkoxythiophene and polyalkylene dioxy thiophene generally adopt enedioxy thiophene monomer or homologue polymerization under normal temperature or high temperature, and enedioxy thiophene and similar different alkylthrophene thereof are valuable compounds to the preparation conductive polymers.The synthetic method of monomer whose mainly is divided into two kinds: thermal decarboxylation reaction (as U.S. Patent No. 2,453103) and catalytic decarboxylation (people such as M.Coffey et al., M.Coffey et al.Synthetic Communications, 26 (11).Add thermal decarboxylation and generally prepare 250 ℃ of high temperature decarboxylation with raw material monomer, yield is low, and the purification of products complex process.Catalytic decarboxylation grows up on thermal decarboxylation technology basis, be catalyzer decarboxylation under 180 ℃ of temperature generally with special copper and oxide compound thereof, its shortcoming is the existence that solvent amine is arranged in the system, brings adverse influence, the purifying technique complexity for the reactions steps of postorder.
A kind of poly-(3,4-dioxy alkylthrophene) preparation method with polyanion mixture and this complex systems mostly is provided in the disclosed document.Or add another kind of compound in this system, but the conductivity of film is also undesirable.Though this mixture has good water dispersible, the transparency of the rear film of filming and electroconductibility deficiency generally only are suitable for low-end product, do not reach the requirement of electronics rank.As preparing the resistivity of film less by its method only to be 102 Ω .cm levels, can not to satisfy 103～105 Ω .cm that the electronics rank requires described in Japanese publication No.JP8-48858 and the No.JP2636968.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of thiophene monomer, products therefrom purity height, the yield height, it is low to consume energy, and operating process is easy.
Another object of the present invention provides the polymerization process of above-mentioned thiophene monomer.
A further object of the present invention provides the application of above-mentioned polymerization process, is about to that polymerisate is used to make through hole wiring board transport layer material and electricity causes generating display spare transport layer material.
The invention provides the monomeric synthetic method of a kind of polythiofuran derivative, raw material filters purifying, decarboxylation and product distillation purification step dewater.Decarboxylic reaction is that raw material is suspended in the unazotized polar solvent, is 100～180 ℃ in temperature, carries out under the condition that has the heavy metal composite catalyst to exist; Raw material is
Perhaps
R wherein
1And R
2Be hydrogen or C
1-C
14Straight chain or branched-chain alkyl, X is the C of straight or branched
1-C
12Alkyl; Reaction product correspondingly is
Perhaps
The heavy metal compound composite catalyst is that mantoquita and oxide compound thereof and chromic salts and oxide compound thereof obtain according to a certain weight ratio, and the ratio of preparation is that the weight ratio of mantoquita and oxide compound and chromic salts and oxide compound thereof is 2～5: 1.
Preferably, temperature of reaction is 110～130 ℃ in the method for the invention.
In the method for the invention, solvent for use can be silicone oil, ketone, ester, ether, sulfoxide, sulphur sulfone or alcohol etc.
In the method for the invention, solvent for use can be polyoxyethylene glycol, phthalic ester, two aryl oxides, tetramethylene sulfone, diaryl sulfone or diaryl sulphoxide etc.Preferably, solvent for use is a kind of in Liquid Macrogol and 400, dibutyl phthalate, ditolyl ether, sulfobenzide, diphenyl sulfoxide, tetramethylene sulfone or the tetramethylene sulfone.
In the method for the invention, the heavy metal compound composite catalyst is that mantoquita and oxide compound thereof and chromic salts and oxide compound thereof obtain according to a certain weight ratio, and the ratio of preparation is that the weight ratio of mantoquita and oxide compound and chromic salts and oxide compound thereof is 2～5: 1.
This is invented described monomer synthesis technique and mainly is suitable for preparing 3,4-alkylidene dioxygen thiophene (3,4-enedioxy thiophene) or 3, the 4-dialkoxythiophene is especially as (5) (EDT, IUPAC name 2,3-dihydrothieno[3,4-b]-1,4-dioxin), structure shown in (6) or (7).
Details are as follows for the monomer preparation process:
1) purification reaction: be about to initially handling of reaction, thereby make its purifying reduce the yield of energy consumption of reaction and raising product.
The crude reaction thing is suspended in the ethylene dichloride, refluxes after 12 hours, mixed solution begins to cool down, and filters to remove unreacted initial thing.Remove excessive ethylene dichloride with rotatory evaporator.Remaining liq was refluxed 1 hour in 10% NaOH.After the cooling, insolubles removes by filter.With the HCl acidifying filtrate of 1N, generate the tawny precipitation, recrystallization in methyl alcohol obtains lurid throw out, is purified decarboxylation raw material.
2) decarboxylic reaction comprises removal and two parts of decarboxylic reaction of moisture in the material.
Dewater: parent material is suspension or is dissolved in entirely and forms the solution shape in the solvent, if institute's water content can be removed in the first step by the underpressure distillation or the form of heating in the material, then need not remove institute's water content in the material separately.This is refluxed as reactor wall built-up water droplet by the structures shape of reactor, then can bring adverse influence to reaction.Thereby also initial reactant can be placed in the vacuum drying oven in 80 ℃ of following freeze-day with constant temperature 1 hour, remove the moisture in the material fully.
Decarboxylation: decarboxylic reaction provided by the invention is to carry out under the condition that high temperature, catalyzer exist, with initial reactant dialkoxythiophene dicarboxylic acid or alkylene oxide group thiophene dicarboxylic acid by stirring suspension in polar solvent or diluent, the principle of selective solvent and thinner is that the boiling point of solvent or thinner generally should be higher than at least 5 ℃ of target product boiling points, and selected solvent should be polarity.Add catalyzer in the system, range of reaction temperature is 100～180 ℃, and optimum range is 130～150 ℃.In this temperature range, carry out decarboxylic reaction, obtain target product.The kind of testing available solvent or thinner has: silicone oil, ketone, ester, ether, sulfoxide, sulphur sulfone or alcohol etc., but the thinner or the solvent of this type of reaction of the uncomfortable cooperation of nitrogenous base solvent, for example quinoline and derivative thereof.Because the existence of amine has adverse influence to the final product of reaction.Concrete can select for use: Baysilone
(Bath woods, Beyer Co., Ltd), polyoxyethylene glycol, phthalic ester, two aryl oxides, tetramethylene sulfone, diaryl sulfone, diaryl sulphoxide etc.And Baysilone wherein
, Liquid Macrogol and 400, dibutyl phthalate, ditolyl ether, sulfobenzide, diphenyl sulfoxide and tetramethylene sulfone be optimal selection again.React selected catalyzer and be generally heavy metal compound, make reaction under relatively low temperature, to carry out.Use maximum be mantoquita and oxide compounds thereof, commonly used has: copper carbonate, copper sulfate, cupric oxide, Red copper oxide or copper hydroxide.The present invention is on this basis to its further improvement, what experiment was adopted is composite catalyst, it is formulated that chromic salts and oxide compound thereof and mantoquita and oxide compound thereof are pressed different ratios, the ratio of preparation is that mantoquita and oxide compound thereof are 2～5: 1 with chromic salts and oxide weight ratio thereof, and the optimum ratio scope is 2.5～4: 1.The use of composite catalyst has further reduced the required optimum temps (110～130 ℃) of decarboxylic reaction.
3) monomer purifying: the distillatory method is generally adopted in the separation of monomeric products, and final product is separated from high boiling solvent or thinner.According to the product purity requirement, carry out repetition rectifying then.Also can use the disposable separation of method of rectifying column to reach the product higher purity, the available method of crossing chromatographic column of further purifying.
The distillatory condition depends on product and the solvent or the purity requirement of the physical properties of thinner and product.The common distillation then mixture of product and thinner at first is distilled out together, can carry out repetition rectifying according to the requirement to the purity of product.Also can use rectifying column that the target product flash liberation is steamed and can obtain higher degree, purity generally can reach 99.5%.Further improve degree of purity of production as need, can adopt the way of chromatographic column drip washing or the method for repeatedly rectification under vacuum to obtain.In general, the simple distillation through fractional column can be to have obtained the product of higher degree.
No matter be that decarboxylic reaction can circulate and carries out in laboratory or the scale operation, new initial substance is joined in the reaction residual, begin new reaction.Contain a large amount of solvents in the residual reactant of circulation back several times, it is steamed from the by product of black, add entry or otherwise make its regeneration in the hope of reusing, this measure has improved the economic benefit of technology to a great extent, has saved the solvent load that accounts for the product cost higher proportion.
The present invention also provides a kind of polymerization process of above-mentioned thiophene monomer, is about to this polythiofuran derivative monomer and adds the stable polythiofuran derivative of aqueous solution high speed stirring formation that contains oxygenant and polyanion electrolyte.The weight ratio of polythiofuran derivative monomer and polyanion electrolyte is 1.0: 1.5～5; Polythiofuran derivative monomer and oxygenant mol ratio are 1: 2～4; The weight percent of water is 5%～30% in the reaction system aqueous solution; Stir speed (S.S.) is 6000～20000rpm; Temperature of reaction is 0-50 ℃; PH value in reaction is 1.0～3.0; Reaction times is 5～30 hours.
The raw material of polyreaction is monomer synthetic product of the present invention, comprises 3,4-alkylidene dioxygen thiophene (3,4-enedioxy thiophene) or 3,4-dialkoxythiophene etc.
Used polyanion electrolyte is can be poly carboxylic acid or poly-sulfonic acid etc. in the polyreaction.Poly carboxylic acid, for example polyacrylic acid, polymethyl acrylic acid and polymaleic acid; Poly-sulfonic acid, for example polystyrolsulfon acid and polyvinyl sulfonic acid.Having adopted polystyrolsulfon acid in one embodiment of the present of invention is polymerization doping ionogen, and its number-average molecular weight scope is 2000-100000, and the weight ratio of its consumption and thiophene is 1.5～5: 1.0.
Used oxygenant can be air, Sodium Persulfate, persulfuric acid, Potassium Persulphate etc. in the polyreaction.The thiophene amount is 1: 2～4 with the ratio of oxygenant molar weight, and in general the consumption of oxygenant should excessive 0.1～2.0 equivalent.Also can use a kind of oxygenant and a kind of mineral acid for finishing polymerization, and the control reaction pH value.The conciliation of solution acidic also can be by adding water miscible organic acid and water miscible mineral acid is finished in the polyreaction, and organic acid can be Phenylsulfonic acid, methylsulfonic acid, and p styrene sulfonic acid, mineral acid can be certain density hydrochloric acid, sulfuric acid and nitric acid.Thereby the pH value of end reaction product is reconciled the requirement that reaches reaction through KOH or NaOH.
The derivative of the Polythiophene that the polyreaction that the present invention describes generates, water insoluble and the organic solvent because of the character of this body structure, so utilize the principle of electrostatic balance in the presence of electrolytical, to make its dispersion polymerization, thereby generate stable colloidal dispersion, so the title reaction system is an aqueous dispersion.The stability of this system is the difficult point in the doped polymeric dispersion process.As from the foregoing, factor affecting such as flow morphology that alr mode causes and polymerization temperature the dispersity of system, and system the most basic be the running balance that reaches system according to the principle of charge balance, thereby monomeric dosage and the structure and the dosage that are used for adulterated polyanionic compound also are the principal elements that influences system stability, be that each reactive material dosage influences each other, and be limited at certain adding in the weight range.At with the control of flow morphology, the present invention adopts the mode of high-speed stirring, it is more even in conjunction with classification polymeric method polymerization to be disperseed simultaneously, helps forming more stable colloidal dispersion.
In the polyreaction, the polymeric reaction temperature scope is preferably 0-30 ℃.
In the polyreaction, polymerization reaction time is preferably 15～30 hours.
The present invention also provides a kind of above-mentioned thiofuran polymer in preparation through hole wiring board transport layer material and the electric application that causes aspect the generating display spare transport layer material.
With the thiofuran polymer finished product colloidal dispersion system after the preparation, standby behind the 450nm film excessively, the optical grade cleaning is carried out on ITO, PET film base material surface, the colloidal dispersion system layering is repeated to coat on the base material.And forced air drying in the time of 80～200 ℃, the time is 60s～15 minute.
Prepared conductive film can be used for through hole wiring board transport layer material, is used for electricity and causes generating display spare transport layer material.
Embodiment
The present invention describes the aggregation colloid dispersion system more specifically by specific embodiment.But the invention is not restricted to these embodiment.
Employed sodium polystyrene sulfonate in example (PSSA, number-average molecular weight=55000, purity＞95%) and polystyrolsulfon acid (PSS, number-average molecular weight=50000, purity＞95%) are provided by Suzhou manization.The polyanionic compound that APS is produced by Nippon NSC Ltd., its number-average molecular weight=60000, above-mentioned substance is used to prepare colloidal dispersion system.
The ion exchange resin that is adopted in the example requires to get final product into home-made highly basic and weak acid ion-exchange resin, and the employing to concrete model in the experiment is not limit.
The reaction of embodiment one catalytic decarboxylation
The 240ml tetramethylene sulfone joins in the reactor, stirs to make it even, adds 50g enedioxy dicarboxylic acid (moisture, content is measured by liquid chromatography), and 2.5g copper carbonate+1.0g chromic oxide.Vacuum tightness is to be heated to 80 ℃ under the 2000Pa, and constant temperature was removed contained humidity in 40 minutes.Charge into nitrogen, continue to be warming up to 110～130 ℃.Mixture reacts 8h under this temperature, until regeneration CO not
2Reaction finishes.Mixture is lowered the temperature a little, vacuumizes, and vacuum tightness is the mixed solution that steams enedioxy thiophene/tetramethylene sulfone under the 2000Pa, 130～150 ℃.
Add the same enedioxy dicarboxylic acid of measuring and a spot of copper carbonate in the residuum of reactor, the tetramethylene sulfone that steams replenishes with new tetramethylene sulfone, and then post-order process is described below:
After three circulations, the mixed solution of 82g enedioxy thiophene/tetramethylene sulfone is through gas-chromatography test enedioxy thiophene 46g (94% yield), HPLC:98.5%.
1HNMR(100MHz，CDCl
3)，δ＝6.20(2H)，3.89(4H)。
13CNMR, (25MHz, CDCl
3): δ (TMS) 141.2 (2C), 64.0 (2C, vinyl carbon).
Use rectifying column to carry out rectifying, generate the higher enedioxy thiophene of purity, HPLC:99.8%, remaining pure tetramethylene sulfone is reused.Compare qualitative with gas-chromatography to product and standard substance.
The round-robin number of times is by the decision of the concentration of initial thing, because the increase of the accumulation of impurity and quantity bring adverse influence can for the generation of target product in the still-process.
Embodiment two catalyst-frees, pure thermal decarboxylation reaction
The 350ml dibutyl phthalate adds in the reaction flask, stirs to add 24g 3,4-ethylidene dioxy base thiophene dicarboxylic acid (content is provided by liquid chromatography).Vacuum tightness is under the 3KPa condition, and it is 140～150 ℃ that heating makes the mixture temperature inside, constant temperature 40min, and the material internal moisture steams in this process.
Charge into nitrogen in the reactor, continue to be heated to 240～250 ℃, constant temperature 24h is until no longer including CO
2Till the generation, reaction finishes, and keeps vacuum cooling, 180 ℃, steam reaction product colourless liquid 3 during 100Pa, 4-alkylidene dioxygen thiophene (EDT or EDOT), product 12g (theoretical yield is 80%), 225 ℃ of EDT boiling points (1000Kpa), HPLC:97.5%.
Two kinds of monomer preparation methods of table 1 relatively
| Experimental technique | Monomer purity monomer yield, % |
| The pure thermodynamics preparation of catalytic preparation | ????99.8?????????94 ????97.5?????????80 |
Embodiment 33, the catalytic decarboxylation reaction of 4-dimethoxy-thiophene
The tetramethylene sulfone of 175ml and 50g are aqueous 70%3, and 4-dimethoxy-thiophene dicarboxylic acid (35g, butt) joins in the reactor and stirs.Add the 4.5g copper hydroxide, mixture is warming up to 85 ℃, under the vacuum tightness 5000Pa, and constant temperature 1.0h.Charge into nitrogen, be warming up to 120 ℃, constant temperature 9.0 hours is until no longer including CO
2Till the generation.Add the 1.5g chromium hydroxide again, mixture continues stirring reaction 3.0h.140～150 ℃ of rectifying column bottom temps, head temperature steams product 3 for 110～140 ℃, and the 4-dimethoxy-thiophene obtains the 19.5g product, and productive rate is 85%.Product IR (KBr, discs) Ar-H, 3115cm
-1 1HNMR (400MHz, CDCl
3, 25 ℃) and δ=3.78 (OCH
3), δ=6.37 (Ar-H).
Embodiment four is a solvent with the Liquid Macrogol
1.5mol enedioxy thiophene-dicarboxylic acid join in the polyoxyethylene glycol solvent of 600ml (molecular-weight average is 300), add the cupric oxide of 33g and the chromic oxide of 10g in the whipping process, utilize the distillation bridge with 3,4-enedioxy thiophene steams, obtaining product purity is 97.7%, and theoretical yield is 96%.Thereby obtain purity with a small amount of washing and be＞99% product.
Embodiment five
In the presence of the oxygenant air, polymeric reaction temperature is a room temperature, with 3 of 1.5g, and 4-enedioxy thiophene and 3.18gC
16E
16Join in the water of 200ml, the high-speed homogenization machine is with the 6000rpm vigorous stirring, and 13.5g APS is dissolved in the 50ml water and joins in the reaction solution, emulsion stirs 24h, and APS: the enedioxy thiophene is 5.64, generates the dispersion system of polymerisate, add each 150 gram of anion-cation exchange resin in succession, behind the induction stirring 3h, remove by filter, getting dispersion system pH is 1.50, (100 ℃ is 1.50% 6h) to solid content, and the particle maximum diameter is less than 200nm, ultimate analysis data: C, 1.47%; H, 11.07%; S＜0.5%.Ion content: Na
+, 350ppm; SO
4 2-, 100ppm.The finished product colloidal dispersion system, code name GH1, stability: under 4 ℃, shelf time＞6 month.
Spin coating: get the polymeric colloid system 100ml that makes, cross the 450nm film after, the tensio-active agent that several milligrams of FSC-100 types that provided by E.I.Du Pont Company are provided is standby.After substrate optics cleans, colloid is spin-coated on the substrate, spin coating speed 1500rpm, after the spin coating as for the loft drier drying, 100 ℃, 5 minutes.Be cooled to room temperature, repeat spin coating 15 times, the oven dry back is to be measured.Table 2 is listed in film thickness and the unification of resistivity value test data in.
Embodiment six
10.65g the enedioxy thiophene, the sodium polystyrene sulfonate of 439g 5.99% (PSSA) and 21.4g oxygenant Sodium Persulfate mix stirring with 2062ml water, at room temperature carry out 10 minutes initial stirring after, add 187mg Fe
2(SO
4)
3, then ultrasonic dispersing smashes, and the pH value of the hierarchy of control is below 1.5, finishes reaction behind the 24h, generates polymer dispersion system, and pH value of solution is 1.50, solid content 1.67%.Ion-exchange techniques is with example five, colloidal dispersion system, code name GH2, under 6 ℃, shelf time＞6 month.Spin coating method and condition are with embodiment five.
Embodiment seven
20g PSS (Mn=50000), the oxygenant Potassium Persulphate of 21.4g and the Fe of 50mg
2(SO
4)
3, in stirring, add 2000ml, add 3 of 8.0g, 4-dimethoxy-thiophene, mixed solution be in high-speed stirring under the room temperature after 10 hours, ultrasonic dispersing 14h, the anionite-exchange resin and the Zeo-karb that then add 100g in succession, mixed solution stir 8h to remove impurity yin, yang ion, remove exchange resin after the filtration, add 10gPSS, vigorous stirring, rotating speed are 8000rpm, and the time is 7h, then the liquid solid content is 2.67%, and pH value of solution is 1.28.Colloidal dispersion system, code name GH3, under 10 ℃, shelf time＞8 month.Spin coating method and condition are with embodiment five.
Embodiment eight
With 20g PSS (Mn=40000), 5.6g 3,4-enedioxy thiophene, 13g oxygenant Potassium Persulphate and 100mg Fe
2(SO4)
39H
2O is dissolved in the deionized water of 1000ml, 20～40 ℃ of following high-speed stirring 8000rpm, reaction 24h, get above-mentioned solution 100ml, deionized water dilution with 1000ml then adds 100g weak base and strong acid ion exchange resin respectively, stirs 6h under the room temperature, remove solid resin after the filtration, the back adds 50ml, 20% PSS, vigorous stirring, speed is 8000rpm, churning time 7h.Final solid content is 2.80%, and pH value of solution is 1.32.Colloidal dispersion system, code name GH4, under 8 ℃, shelf time＞6 month.The method of spin coating and condition are with embodiment five.
Each dispersion polymerization system films test result of table 2
| Code name | Butt film thickness (μ m) | The film square (Ω/) | Film resiativity (Ω .cm) |
| ????GH1 | ????0.72 | ????1.04×10 7 | ????7.5×10 2 |
| ????GH2 | ????0.69 | ????1.39×10 7 | ????9.6×10 2 |
| ????GH3 | ????0.74 | ????1.31×10 9 | ????0.97×10 5 |
| ????GH4 | ????0.75 | ????1.33×10 9 | ????1.01×10 5 |
Claims (10)
1. the preparation method of a thiophene monomer, comprise that raw material filters purifying, decarboxylation and product distillation purification step dewater, it is characterized in that decarboxylic reaction is that raw material is suspended in the unazotized polar solvent, be 100～180 ℃ in temperature, carry out under the condition that has the heavy metal composite catalyst to exist; Raw material is
Perhaps
, R wherein
1And R
2Be hydrogen or C
1-C
14Straight chain or branched-chain alkyl, X is the C of straight or branched
1-C
12Alkyl; Reaction product correspondingly is
Perhaps
The heavy metal compound composite catalyst is that mantoquita and oxide compound thereof and chromic salts and oxide compound thereof obtain according to a certain weight ratio, and the ratio of preparation is that the weight ratio of mantoquita and oxide compound and chromic salts and oxide compound thereof is 2～5: 1.
2. the method for claim 1 is characterized in that temperature of reaction is 110～130 ℃.
3. the method for claim 1, solvent for use is any in silicone oil, ketone, ester, ether, sulfoxide, sulphur sulfone or the alcohol in it is characterized in that reacting.
4. method as claimed in claim 3, solvent for use is any in polyoxyethylene glycol, phthalic ester, two aryl oxides, tetramethylene sulfone, diaryl sulfone or the diaryl sulphoxide in it is characterized in that reacting.
5. the polymerization process of the described thiophene monomer of claim 1, be about to this polythiofuran derivative monomer and add the stable polythiofuran derivative of aqueous solution high speed stirring formation that contains oxygenant and polyanion electrolyte, the weight ratio that it is characterized in that thiophene monomer and polyanion electrolyte is 1.0: 1.5～5; Thiophene monomer and oxygenant mol ratio are 1: 2～4; The weight percent of water is 5%～30% in the reaction system aqueous solution; Stir speed (S.S.) is 6000～20000rpm; Temperature of reaction is 0-50 ℃; PH value in reaction is 1.0～3.0; Reaction times is 5～30 hours.
6. polymerization process as claimed in claim 5 is characterized in that polyanion electrolyte is poly carboxylic acid or poly-sulfonic acid.
7. polymerization process as claimed in claim 5, the oxygenant that uses in it is characterized in that reacting is in air, Sodium Persulfate, persulfuric acid, the Potassium Persulphate one or more.
8. polymerization process as claimed in claim 5 is characterized in that the polymeric reaction temperature scope is 0-30 ℃.
9. polymerization process as claimed in claim 5 is characterized in that polymerization reaction time is 15～30 hours.
10. the product of the described polymerization process of claim 5 is in preparation through hole wiring board transport layer material and the electric application that causes aspect the generating display spare transport layer material.
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| CN101616950B (en) * | 2006-12-21 | 2012-05-23 | 拜尔技术服务有限责任公司 | Method for obtaining thiophene oligomers |
| CN101488064B (en) * | 2008-01-15 | 2011-06-15 | 松下电器产业株式会社 | Touch panel, and movable contact unit and switch using the same touch panel |
| US8378992B2 (en) | 2008-01-15 | 2013-02-19 | Panasonic Corporation | Touch panel, and movable contact unit and switch using the same touch panel |
| CN102351841A (en) * | 2011-09-21 | 2012-02-15 | 天津理工大学 | Preparation method of 1,4-bis[di(2-thienyl)] methylbenzene |
| TWI577776B (en) * | 2012-12-17 | 2017-04-11 | Mitsubishi Plastics Inc | No substrate on both sides of the adhesive sheet |
| CN104781360B (en) * | 2012-12-17 | 2017-09-22 | 三菱化学株式会社 | Without base material double-sided adhesive sheet |
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