CN100569828C - Disperse system of nano composition colloid of polythiophene and preparation method thereof - Google Patents
Disperse system of nano composition colloid of polythiophene and preparation method thereof Download PDFInfo
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- CN100569828C CN100569828C CNB2005100249513A CN200510024951A CN100569828C CN 100569828 C CN100569828 C CN 100569828C CN B2005100249513 A CNB2005100249513 A CN B2005100249513A CN 200510024951 A CN200510024951 A CN 200510024951A CN 100569828 C CN100569828 C CN 100569828C
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Abstract
The invention belongs to technical field of polymer materials, be specially a kind of novel disperse system of nano composition colloid of polythiophene and preparation method thereof, and the method that this colloidal dispersion system is prepared into nano thin-film.The original monomer of this colloidal dispersion system is a polythiofuran derivative, adds deionized water, polyphosphazene polymer anion electrolyte, alcohols, oxygenant, impacts through high velocity air, stirs, and forms the bubble homogeneous system; After reaction finished, ultrasonic dispersing formed stable colloidal dispersion system again.This colloidal dispersion system is repeated to coat on the substrate with spin-coating method, and self-assembly forms film.This film has excellent conductivity, has expanded its range of application greatly.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of novel disperse system of nano composition colloid of polythiophene and preparation method thereof.The present invention also relates to the method for this nanocomposite dispersions system being made nano thin-film simultaneously.
Background technology
21 century, the high speed development of information, biotechnology, the energy, environment, advanced manufacturing technology and national defence must propose new demand to material, and the miniaturization of element, intellectuality, high integrated, high-density storage and ultrafast transmission etc. are more and more littler to the dimensional requirement of material.Nano material and nanostructure be the most dynamic in the current novel material research field, the future economy and social development are had the very research object of material impact, also be the most active in the nanosecond science and technology, the important component part of approaching application.In recent years, nano material and nanostructure have obtained conspicuous achievement.
At present, utilize colloidal suspension to prepare the nanoparticle of multiple metal oxide, such as SnO
2, ZnO, WO
3, TiO
2And Fe
2O
3Studies show that,, can realize " design as required " of nanoparticle character by the control of double conductor precursor colloid for preparing condition.Thereby nanoparticle source of parents colloid relies on the big specific surface area of composite nanoparticle, orderly particle structure to have the character of many uniquenesses, for example photochromic, electrochromism, photochemical catalysis and photoelectrochemistry character etc.
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, novel 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.For further reaching the excellent specific property that its conductive stability utilizes above-mentioned colloidal dispersion nanoparticle to exist simultaneously, we courageously adopt nanometer composite technology to combine with organic synthesis technology, electrochemical properties was further strengthened after plan made material filming, improved the stability of system simultaneously.The result proves that electrochemistry is obviously unique, relies on its outstanding conductivity, and we can be called " conducting metal " with the novel Polythiophene electro-conductive material of this kind.
Therefore as can be known, novel Polythiophene conducting polymer derivative is valuable compound, and a kind of poly-(3,4-dioxy alkylthrophene) preparation method with polyanion mixture and this complex systems mostly is provided in the disclosed document.But the colloidal dispersion particle structure is not done modification or only add the mixing that another kind of compound reaches a kind of thing amount state in system, the conductivity that makes film with this kind colloid is unsatisfactory, though have good water dispersible, but the transparency of the rear film of filming and electroconductibility deficiency, generally only be suitable for low-end product, it is low not reach the requirement of electronics rank, material use efficiency and industrial benefit.As described in Japanese publication No.JP8-48858 and the No.JP2636968 to prepare the resistivity of film less by its method only be 10
2Ω .cm level can not satisfy 10 of electronics rank requirement
3～10
5Ω .cm.
The present invention relates to through nanoparticle compound polymeric colloid system, after making nano thin-film by specific method, not only inherited the character of many uniquenesses in the source of parents colloid, the ins and outs of while combining nano orientation film, improved the conductivity of its film greatly, made the nano thin-film resistivity that makes 10
2-10
6Adjustable in the Ω .cm scope.Further enlarged the practical ranges of this kind colloid water prose style free from parallelism system.
Summary of the invention
The purpose of this invention is to provide a kind of novel disperse system of nano composition colloid of polythiophene and preparation method thereof, make resulting colloidal dispersion both have the performance of electro-conductive material itself, the chemical property that has the nano material uniqueness again, show more superior electrical conductivity energy after making it make film, can be applied in the reality widely.
Another object of the present invention provides the method for this kind disperse system of nano composition colloid of polythiophene being made nano thin-film.
Novel disperse system of nano composition colloid of polythiophene provided by the invention, the original monomer of its polymerization system are polythiofuran derivative, and its structure is as follows:
R wherein
1And R
2Be hydrogen or C
1-C
14Straight chain or branched-chain alkyl, X is C
1-C
12The alkyl of straight or branched; The colloidal dispersion system main substance that obtains also correspondingly is corresponding with it Polythiophene.Starting monomer more preferably is 3, and 4-alkylidene dioxygen thiophene (3,4-enedioxy thiophene and 3,4-dialkoxythiophene etc.
The preparation method of novel disperse system of nano composition colloid of polythiophene provided by the invention is as follows: the polythiofuran derivative monomer is joined in the deionized water, and adding polyphosphazene polymer anion electrolyte and alcohols material, gas shock is stirred and is formed small bubble homogeneous system, and adds oxygenant; Reconcile system pH with the soda acid mediator agent, stir simultaneously, reaction; Reaction finishes the back system is carried out ultrasonic dispersing, makes reaction system form stable colloidal dispersion system, and the dispersed particle maximum diameter is less than 100nm in the colloidal dispersion.
In the nano combined system process of preparation of the present invention, the weight percent of water is 5-30% in the reaction system deionized water solution; The part by weight scope of polythiofuran derivative monomer and polyphosphazene polymer anion electrolyte is 1: 1.5-1: 5, and the oxygenant mol ratio of polythiofuran derivative monomer and adding is 1: 2～1: 4; The gas shock stir speed (S.S.) is 6000～20000rpm; The conditioned reaction system pH is 1.0～5.0, is preferably 1.0-3.0; The stirring reaction temperature is 15-70 ℃, is preferably 20-40 ℃; Duration of the reaction is 5～30h, is preferably 15-24h; The ultrasonic dispersing time length is 1-5h, is preferably 3-4h.
The polyphosphazene polymer anion electrolyte of mentioning in the colloid for preparing reaction can be poly carboxylic acid or poly-sulfonic acid etc.Poly carboxylic acid, for example polyacrylic acid, polymethyl acrylic acid and polymaleic acid; Poly-sulfonic acid, for example polystyrolsulfon acid and polyvinyl sulfonic acid.Wherein be preferably poly-sulfonic acid series.Its number-average molecular weight scope of used polymer dielectric is 5000-200000, is preferably 50000-150000.
Mention the alcohols material of adding in the colloid for preparing reaction, be mainly polyoxyethylene glycol, methyl alcohol or ethanol etc. are preferably Polyethylene Glycol-600, and polyoxyethylene glycol 1200.
Used oxygenant can be air, purity oxygen, Sodium Persulfate, persulfuric acid, Potassium Persulphate or ammonium persulphate etc. in the colloid for preparing reaction.Thiophene starting monomer amount is 1: 2～1: 4 with the ratio of oxygenant molar weight, and in general the consumption of oxygenant should excessive 0.1～2.0 equivalent.Also a kind of oxygenant and a kind of mineral acid can be used in combination the pH value of control reaction system when finishing polyreaction.
Solution soda acid mediator agent can adopt water miscible organic acid and water miscible mineral acid in the colloid for preparing reaction, and organic acid can be Phenylsulfonic acid, and methylsulfonic acid or p styrene sulfonic acid, mineral acid can be hydrochloric acid, sulfuric acid or nitric acid.The KOH that is preferably, NaOH and hydrochloric acid, low-concentration sulfuric acid.
The present invention also provides the method for this kind composite nano-polymers colloidal dispersion being made film, and its step is as follows:
With the composite Nano colloidal dispersion system of making, it is standby to carry out membrane filtration (filter opening 120-200nm) back.Clean process is carried out on ITO, PET film base material surface, make its surface reach the optics atomic level, base material is dipped in carries out surface-active-treatment in the tensio-active agent.With the colloidal dispersion system for preparing, the method layering of using spin coating repeats to coat on the base material, makes it carry out the directed self assembling process of film at substrate surface; Make its vacuum-drying on heating platform, temperature is 80～200 ℃, and the time is 1～15min.The 1.0-3.0h that then anneals in 200-400 ℃ of following air promptly makes with conductive surface and has the nano structural conductive film that directly contacts.Film thickness is between 15-100nm, by the number of times control that repeats to be coated with.
In the aforesaid method, the mass concentration scope of described colloidal dispersion system is 0.5-10%, is preferably 1-4%.Spin coating process medium speed is 2500-5000rpm, is preferably 3000-4000rpm.The used tensio-active agent of substrate surface is conventional tensio-active agent.
Prepared electrical-conductive nanometer film can be used for through hole wiring board transport layer material, is used for electro-luminescence display device transport layer material, also can be used as above-mentioned base material antistatic film coating, also can be used as anode material and replaces ITO (tin indium oxide) conductive glass.
Embodiment
The present invention by specific embodiment to aggregation colloid dispersion system and nano thin-film performance thereof with and preparation method thereof describe more specifically.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 Shandong Zibo star chemical industry company limited.
The super infiltration technology of ion is adopted in the removal of yin, yang ion and small organic molecule among the embodiment.
First part: the preparation of disperse system of nano composition colloid of polythiophene
Embodiment 1
In the presence of the oxygenant air, polymeric reaction temperature is a room temperature, and with 3 of 1.5g, 4-enedioxy thiophene and 3.18g polyvinyl sulfonic acid (Mn=120000) join in the deionized water of 200ml, add the 0.15g Polyethylene Glycol-600 simultaneously, gas shock blasts air, and stir speed (S.S.) is 6000rpm, adds the soda acid modulator, hierarchy of control pH value is below 2, stirring reaction time 15h, 60 ℃ of temperature of reaction, last ultra-sonic dispersion 3.0h.Reaction finishes to generate black-and-blue polymer dispersion.
With the adverse current dialysis in the dialysis bag (maximum dialysis Mn=is 7000) after active processing of packing into of this dispersion liquid, recording system pH behind the 30h is 1.50, and (100 ℃ is 1.50% 6h) to solid content.Ion content: Na
+, 350ppm; SO
4 2-, 100ppm.The particle maximum diameter is less than 100nm.
Get its ultimate analysis data: C of finished product colloidal dispersion system, 1.47%; H, 11.07%; S＜0.5%.Code name NM1, stability: under 4 ℃, shelf time＞6 month.
Embodiment 2
The enedioxy thiophene of 10g, the sodium polystyrene sulfonate of 400g 5.99% (PSSA) mixes stirring with the 2062ml deionized water, after the initial stirring of carrying out 10min under the room temperature, add 3.0g polyoxyethylene glycol 1200 in system, high velocity air impacts, and stir speed (S.S.) reaches 12000rpm, add 22.5g oxygenant Potassium Persulphate, the pH value that adds a certain amount of soda acid mediator agent hierarchy of control simultaneously in reaction process is below 3.0, stirring reaction time 24h, temperature of reaction 20-40 ℃.Ultra-sonic dispersion 5h again.Reaction finishes the blue-black watery polymer dispersion of back generation, and the system pH of recording is 2.5, solid content 1.67%, and the particle maximum diameter is less than 100nm.The removing method of small organic molecule and foreign ion gets colloidal dispersion system, ion content: Na with embodiment 1
+, 250ppm; SO
4 2-, 80ppm.The particle maximum diameter is less than 100nm.Code name NM2, under 6 ℃, shelf time＞6 month.
Embodiment 3
20g PSS (Mn=50000) is added the 2000ml deionized water, add 3 of 8.0g simultaneously, the 4-dimethoxy-thiophene, behind the initial stirring at low speed 20min, the oxygenant ammonium persulphate that adds 21.4g, mixed solution high velocity air under room temperature impacts, high-speed stirring (8000rpm) control pH value behind the reaction 20h, adds 10g PSS below 4 once more, ultrasonic dispersing 4h, get black-and-blue dispersion liquid, the removing method of small organic molecule and foreign ion such as embodiment 1 get final colloidal dispersion system after the processing, recording the liquid solid content is 2.67%, and pH value of solution is 1.28.Ion content: Na
+, 300ppm; SO
4 2-, 90ppm.The particle maximum diameter is less than 100nm.Code name NM3, under 10 ℃, shelf time＞8 month.
The comparative example of example 3 (non-nano compound dispersing agent FNM)
20g PSS (Mn=50000) is added the 2000ml deionized water, add 3 of 8.0g simultaneously, the 4-dimethoxy-thiophene behind the initial stirring at low speed 20min, adds the oxygenant Sodium Persulfate of 21.4g and the Fe of 350mg
2(SO
4)
3Mixed solution is after stirring (3500rpm) 20h under the room temperature, add 10g PSS once more, after keeping stirring 4h, get the black-and-blue dispersion liquid of product, the removing method of small organic molecule and foreign ion such as embodiment 1 get final colloidal dispersion system after the processing, recording the liquid solid content is 2.35%, and pH value of solution is 2.0.
Ion content: Na
+, 320ppm; SO
4 2-, 85ppm.The particle maximum diameter is less than 360nm.Code name FNM, under 10 ℃, shelf time＞8 month.
The preparation of second section self-assembled nanometer film
Embodiment 4
With the nano combined colloidal dispersion system NM3 in the foregoing description 3, mass concentration is 1.67%, carry out preliminary membrane filtration (200nm) after.Base material I TO (tin indium oxide) is handled by conventional cleaning procedure, make its surface reach the optics atomic level, ito glass after handling is dipped in carries out surface treatment in the silicone surfactant, the spin coating rotating speed is 3000rpm, vacuum-drying on heating platform after the coating, temperature is 90 ℃, time of drying 90s, expose annealing 1.5h in 250 ℃ of following air, make film, to record butt single film layer thickness be 20nm to a spin coating of film after film thickness is surveyed instrument, repeat spin coating 5 times after gained butt film thickness between 80-100nm.
The comparative example 4
With same treatment process, the non-nano matrix material colloidal dispersion system FNM under the similarity condition is also made corresponding film, repeat after the spin coating 5 times gained film thickness and film resiativity test comparison uniform data and list in the following table 1.
Table 1 colloidal dispersion system makes the films test comparing result
Data can clearly show in the table, composite Nano colloidal particle NM3 makes its resistivity value of nano thin-film and obviously is better than the nano thin-film that non-nano particle FNM makes, can widen in a wider context between resistivity zone, thereby enlarge the range of application of product, be particularly useful for electric hole transport material and electron buffer layer material.
Embodiment 5
Made colloid among embodiment 1 and the embodiment 2 is also made film by identical method, and spin coating liquid mass concentration all is adjusted to 1.67%, and rotating speed is 3000rpm.Repeating after the spin coating 5 times gained film thickness and film resiativity test data lists in the following table 2.
Table 2 film resiativity test result
The Different Preparation of film and the different preparation method of nano combined colloidal dispersion can have certain influence to film forming resistivity.
Claims (7)
1, a kind of disperse system of nano composition colloid of polythiophene is characterized in that the original monomer structure of polymerization system is as follows:
R wherein
1And R
2For hydrogen or be C
1-C
14The straight or branched alkyl, X is C
1-C
12The alkyl of straight or branched;
And adopt following method to prepare: above-mentioned original monomer is joined in the deionized water, add polyphosphazene polymer anion electrolyte and alcohols material subsequently, gas shock is stirred and is formed small bubble homogeneous system, and adds oxygenant; Reconcile system pH with the soda acid mediator agent, stir simultaneously, reaction; Reaction finishes the back system is carried out ultrasonic dispersing, makes reaction system form stable colloidal dispersion system, and the dispersed particle maximum diameter is less than 100nm in the colloidal dispersion;
Wherein: the weight percent of water is 5-30% in the reaction system deionized water solution; The part by weight scope of original monomer and polyphosphazene polymer anion electrolyte is 1: 1.5-1: 5, and the oxygenant mol ratio of original monomer and adding is 1: 2～1: 4; The gas shock stir speed (S.S.) is 6000～20000rpm; The conditioned reaction system pH is 1.0～5.0; The stirring reaction temperature is 15-70 ℃; Duration of the reaction is 5～30h; The ultrasonic dispersing time length is 1-5h; The polyphosphazene polymer anion electrolyte adopts poly carboxylic acid or poly-sulfonic acid, and its number-average molecular weight is 5000-200000; Alcohols material is polyoxyethylene glycol, methyl alcohol or ethanol.
2, a kind of preparation method of disperse system of nano composition colloid of polythiophene according to claim 1, it is characterized in that concrete steps are as follows: described original monomer is joined in the deionized water, and adding polyphosphazene polymer anion electrolyte and alcohols material, gas shock is stirred and is formed small bubble homogeneous system, and adds oxygenant; Reconcile the system pH value with the soda acid mediator agent, stir simultaneously, reaction; Reaction finishes the back system is carried out ultrasonic dispersing, makes reaction system form stable colloidal dispersion system, and the dispersed particle maximum diameter is less than 100nm in the colloidal dispersion;
Wherein: the weight percent of water is 5-30% in the reaction system deionized water solution; The part by weight scope of original monomer and polyphosphazene polymer anion electrolyte is 1: 1.5-1: 5, and the oxygenant mol ratio of original monomer and adding is 1: 2～1: 4; The gas shock stir speed (S.S.) is 6000～20000rpm; The conditioned reaction system pH is 1.0～5.0; The stirring reaction temperature is 15-70 ℃; Duration of the reaction is 5～30h; The ultrasonic dispersing time length is 1-5h; The polyphosphazene polymer anion electrolyte adopts poly carboxylic acid or poly-sulfonic acid, and its number-average molecular weight is 5000-200000; Alcohols material is polyoxyethylene glycol, methyl alcohol or ethanol.
3, preparation method according to claim 2 is characterized in that said oxygenant adopts air, purity oxygen, Sodium Persulfate, persulfuric acid, Potassium Persulphate or ammonium persulphate.
4, preparation method according to claim 2 is characterized in that said soda acid mediator agent adopts Phenylsulfonic acid, methylsulfonic acid or styrene sulfonic acid, perhaps adopts hydrochloric acid, sulfuric acid or nitric acid.
5, a kind of the described disperse system of nano composition colloid of polythiophene of claim 1 is prepared the method for nano thin-film, it is characterized in that concrete steps are as follows:
Film base material is carried out clean and surface-active-treatment; Disperse system of nano composition colloid of polythiophene is carried out membrane filtration, and the filter opening of film is 120-200nm, and the mass concentration of control colloidal dispersion system is 0.5-10%; With spin-coating method the colloidal dispersion system layering is repeated to coat on the base material, make it carry out the directed self assembling process of film at substrate surface; The rotating speed of spin coating is 2500-5000rpm; Make its vacuum-drying then on heating platform, temperature is 80-200 ℃, 1 minute-15 minutes time; 1-3h at last anneals in 200-400 ℃ of following air.
6, the method for preparing nano thin-film according to claim 5, the thickness that it is characterized in that film is 15-100nm, by the number of times control that repeats to be coated with.
7, the method for preparing nano thin-film according to claim 5, the mass concentration that it is characterized in that described colloidal dispersion system is 1-4%.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1953178B1 (en) * | 2005-11-17 | 2018-06-13 | Heraeus Deutschland GmbH & Co. KG | Process for producing aqueous dispersion of composite of poly(3,4-dialkoxythiophene) with polyanion |
| CN100519634C (en) * | 2007-03-12 | 2009-07-29 | 中国科学院长春应用化学研究所 | Conjugated polymer and nano-particle composite thin film and its production |
| DE102008005568A1 (en) | 2008-01-22 | 2009-07-23 | H.C. Starck Gmbh | Process for the preparation of conductive polymers |
| CN101407575B (en) * | 2008-12-08 | 2011-08-17 | 北京服装学院 | High dispersibility nano-scale poly (3,4-ehtylene dioxythiophene), preparation and use thereof |
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