CN100594560C - Process for preparing electroconductive coatings - Google Patents

Process for preparing electroconductive coatings Download PDF

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CN100594560C
CN100594560C CN200480023731A CN200480023731A CN100594560C CN 100594560 C CN100594560 C CN 100594560C CN 200480023731 A CN200480023731 A CN 200480023731A CN 200480023731 A CN200480023731 A CN 200480023731A CN 100594560 C CN100594560 C CN 100594560C
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reaction medium
compound
pedot
polymer
pss
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CN1839448A (en
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F·罗维特
E·范蒂洛
B·格勒嫩达尔
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Agfa Gevaert NV
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
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  • Wood Science & Technology (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

An aqueous dispersion of latex particles, said latex particles containing a polymer containing monomer units according to formula (I), in which R<1> and R<2> independently of one another represent hydrogen or a C1-5-alkyl group or together form an optionally substituted C1-5-alkylene residue and at least one polyanion compound, said latex having a primary particle size of less than 40 nm and saiddispersion contains an organic compound containing a dior polyhydroxy- and/or carboxy groups or amide or lactam group or an aprotic compound with a dielectric constant, [epsilon], >= 15, characterizedin that said latex particles contain said at least one polyanion compound and said polymer in a weight ratio of at least 4; a process for preparing an electroconductive coating comprising the steps of: preparing an aqueous solution or dispersion of the abovementioned polymer by polymerization with an initiator in a reaction medium in the presence of at least one polyanion compound under oxidizingor reducing conditions.

Description

The method for preparing conductive coating
Invention field
The present invention relates to prepare the method for conductive coating.
Background of invention
Polythiophene is widely studied owing to its noticeable electricity and/or optical property.Polythiophene becomes after chemistry or electrochemical oxidation or reduction and has conductivity.The conductivity that they may ultimately reach is by the stereoregularity of thiophene monomer polymerization in their chemical composition, polythiophene chain and their pi-conjugated length decision.When thiophene that the unsubstituted thiophene of polymerization or 3-and 4-position are replaced by same group, can not produce this stereoregularity problem.
EP-A 339340 discloses the method for the polythiophene of the construction unit that contains following formula and the preparation of the oxidation polymerization by corresponding thiophene thereof,
Figure C20048002373100061
Wherein A represents the optional C1-C4 alkylidene that replaces.
EP-A 440957 discloses the dispersion liquid of polythiophene, and this polythiophene is in the presence of polyanionic compound, by the construction unit formation of following formula (I),
Figure C20048002373100062
R wherein 1And R 2The independent separately C1-C4 alkylidene of representing hydrogen or C1-C4 alkyl or forming optional replacement together.In the embodiment of this patent, disclose in detail in the presence of poly-(styrene sulfonic acid), 3, the polymerization of 4-Ethylenedioxy Thiophene [EDOT] in water, wherein 3, the 4-Ethylenedioxy Thiophene is 1: 1.29 (embodiment 2), 1: 2.2 (embodiment 7 and 8), 1: 4 (embodiment 1,3,4 and 10), 1: 6 (embodiment 5) and 1: 8.33 (embodiment 6) with the weight ratio of poly-(styrene sulfonic acid).
In October calendar year 2001, disclose the high resistivity PEDOT/PSS that in passive component OEL, reduces cross-talk among the paper OEL3-3 that Elschner etc. are to be delivered on the ASIADISPLAY/IDW ' 01 that Japanese Nagayo holds, and listed standard BAYTRON TMP and BAYTRON TMThe characteristic of P type AI4083 and CH8000, duplicate as follows:
BAYTRON P type Resistance coefficient [Ω-cm] Particle size distribution center [nm] PPS: PEDOT weight is formed
Standard 1 110 2.5∶1
VP AI4083 500-1000 55 6∶1
VP CH8000 70,000-200,000 20 20∶1
Elschner etc. are report further: only move on to 20nm by the particle size distribution center from about 100nm, conductance is than standard BAYTRON TMP has reduced several magnitude, finds that simultaneously gel particle is of a size of water-soluble bloated state and dehydration back size is littler.The existing trade literature of BAYER company has provided this three kinds of BAYTRON TMThe feature of P grade:
Figure C20048002373100071
The aqueous dispersions of PEDOT/PSS can be available from BAYER company, and commodity are called BAYTRON TMP.Find to analyze the standard BAYTRON that (as P.Adriaensens etc. at Polymer, 43 volumes, the 7003-7006 page or leaf is described in 2002) determines with 13C NMP TMMol ratio among the P is 2.7 (being equivalent to weight ratio is 3.50), finds available from the mol ratio in the PEDOT/PSS standard water dispersion liquid of AGFA-GEVAERT N.V. to be 2.1 (being equivalent to weight ratio is 2.72).
Table 1
The PEDOT type The initial aromatic carbon atom intensity of PSS The initial aliphatic carbon atom intensity of PSS The average initial carbon atom intensity of PSS The initial ether carbon atom of PEDOT intensity PSS/PEDOT
BAYTRON TMP sample 1 445 454 449.5 164 2.7
BAYTRON TMP sample 2 246 260 253 85 3.0
AGFA-GEVAERT PSS/PEDOT dispersion liquid 446 493 470 226 2.1
M.Lefebvre etc. are at Chem.Materials, 11 volumes, the 262-268 page or leaf, 1999 have reported from the conductance of the PEDOT/PSS of the water of EDOT and NaPPS and acetonitrile (AN) solution (PSS is 0.24 to 3.33 with the ratio of PEDOT) preparation along with PSS: the minimizing of PEDOT ratio improves, this expectation with those skilled in the art is consistent, and this is because due to the concentration of conductive compositions PEDOT own uprises.
Solvent for use The PSS that obtains: PEDOT ratio Initial conductance [Scm -1]
AN/ water 0.48 1.3
AN/ water 0.67 1.0
AN/ water 0.71 1.5
AN/ water 0.91 0.3
AN/ water 1.0 2.5
AN/ water 3.33 6×10 -3
Water 0.24 9.9
Water 2.0 0.3
Water 2.5 0.4
EP-A-686662 discloses following A) and mixture B), and the electrically-conducting paint that obtains thus, its resistance improved preferably to＜300 Ω/sq by adjusting;
A wherein) have the neutral polythiophene of the constitutional repeating unit of formula (I),
Figure C20048002373100091
R wherein 1And R 2Independent separately hydrogen or C1-C4 alkyl or the optional C1-C4 alkylidene that replaces of expression together represent, the methylene that preferably optional alkyl replaces, 1 of optional C1-C12 alkyl or phenyl replacement, 2-ethylidene or 1, the 2-cyclohexylidene and
B) contain two or the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-.
In addition, the embodiment among the EP-A 686662 discloses the polymerization of EDOT in water in the presence of poly-(styrene sulfonic acid), and EDOT is 1: 3.57 with the weight ratio of poly-(styrene sulfonic acid).
WO 03/001299A discloses the material of preparation conductive pattern, described material comprises supporter and exposure differentiable element, it is characterized in that described exposing quantity differentiable element comprises contains polyanion and replacement or the not polymer of substituted thiophene or the outermost layer and the contiguous described outermost optional second layer of copolymer, the wherein said outermost layer and/or the described optional second layer contain photosensitive composition, can change the mobility of described outermost exposure part with respect to described outermost not exposure part by this photosensitive composition of exposure.The also open conductance that improves by the following method of WO 03/001299A: by as contact high boiling liquid (as contain two or the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-), optional subsequently under higher temperature, preferred 100 to 250 ℃, heated preferred 1 to 90 second.Perhaps, under the situation of the aprotic compound (as the N-methyl pyrrolidone) of dielectric constant 〉=15, can adopt to be lower than 100 ℃ temperature.Can observe with polythiophene that this conductance improves and this conductance raising meeting takes place or generation subsequently in the outermost layer preparation process.The particularly preferred liquid that is used for this processing is N-methyl pyrrolidone and diethylene glycol (DEG), as disclosed among EP-A 686662 and the EP-A 1003179.The PEDOT of PEDOT/PSS dispersion liquid that is used for all embodiment of WO 03/001299A: the PSS weight ratio is 1: 2.4, and with the narrow diameter distribution of CPS disc type centrifugal determination, maximum particle diameter is that 25nm, average grain diameter are 30-50nm.
EP-A 1003179 discloses the method for preparing polymeric, conductive layer on object, and this method comprises the steps: to prepare the Aquo-composition of the aprotic compound that contains polythiophene, polyanionic compound and DIELECTRIC CONSTANT 〉=15; Described composition is coated to cambium layer on the described object; Dry described layer to be to form conductive polymer coating on described object, it is characterized in that described object and described layer remain below under 100 ℃ the temperature and the maximum resistance coefficient of described conductive polymer coating is 2k Ω/sq.In addition, the embodiment among the EP 1003179 discloses the polymerization of EDOT in water in the presence of poly-(styrene sulfonic acid), and EDOT is 1: 2.46 with the weight ratio of poly-(styrene sulfonic acid).
In addition, Kim etc. are at Proceedings of SPIE, 4464 volumes, and the 85-92 page or leaf, having reported in 2002 and having adopted average grain diameter is the BAYTRON of 25nm-75nm TMP is as raw material, and by adding a spot of polyalcohol such as glycerol, the conductance of PEDOT/PSS can significantly improve and can not lose optical clarity.Pettersson etc. are at Organic Electronics, and 3 roll up, and the 143-148 page or leaf has been reported same employing BAYTRON TMP is raw material (be PEDOT: the PSS weight ratio is 1: 2.5), and by adding sorbierite, the conductance of PEDOT/PSS can improve and can not lose transparency.
The common disadvantage of the conducting polymer that has prepared up to now and studied is that its conductance is still too low for some application, its visible light transmittance rate not high enough and/or they can not process.
The object of the invention
Therefore an aspect of of the present present invention provides 3,4-alkylene dioxo base-thiophene, described 3,4-alkylene dioxo base-thiophene can be gathered (3 after polymerization, 4-alkylene dioxo base-thiophene), described poly-(3,4-alkylene dioxo base-thiophene) have high conductivity, high transmission of visible light and/or good processing properties after oxidation or reduction.
To become apparent by the additional objects and advantages of the present invention of description hereinafter.
Summary of the invention
Open in undocumented European applicant nr.EP 01000780: the sheet resistance of layer that contains PEDOT/PSS along with reaction medium in oxygen concentration reduction and reduce, be lower than 3 milligrams of oxygen/rise the PEDOT/PSS dispersion liquid that makes in the reaction medium of reaction medium at oxygen concentration and have best surface resistance.Therefore, the preparation method of research PSS/PEDOT latex to this latex preparation layer Effect on Performance the time, importantly adopt the PSS/PEDOT latex that in the reaction medium that contains close concentration oxygen, makes.The inventor is unexpected to be found, with M.Lefebvre etc. at Chem.Materials, 11 volumes, the 262-268 page or leaf, report among the paper OEL3-3 that Elschner etc. is to be delivered on the ASIA DISPLAY/IDW ' 01 that Japanese Nagayo holds with October calendar year 2001 in 1999 (these reports point out that conductivity is along with PSS: the raising of PEDOT ratio and reduce) is different, if have special additive such as N-methyl-pyrrolidones and polyol such as diethylene glycol (DEG) in the dispersion liquid, the sheet resistance of the layer that makes with the aqueous dispersions of PEDOT/PSS latex is along with PSS: the raising of PEDOT ratio and reducing, the aqueous dispersions of wherein said PEDOT/PSS latex makes in the reaction medium that contains specific concentrations oxygen.Although as can be known: when the layer that contains PSS/PEDOT latex is heated from EP-A 0682662 and EP-A 1003179, this additive has improved the conductance of described layer, unexpected fully is: when the PSS/PEDOT ratio was higher, when promptly PEDOT concentration was lower, conductance improves can be bigger.
Adopt the aqueous dispersions of latex particle to realize each side of the present invention, described latex particle contains polymer and at least a polyanionic compound of being made up of the construction unit that comprises monomeric unit shown in the formula (I),
R wherein 1And R 2Independent separately expression hydrogen or C 1-5Alkyl or form the optional C that replaces together 1-5Alkylidene, the primary particle size of described latex is less than 40nm, described dispersion liquid contains with two or the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-or the aprotic compound of DIELECTRIC CONSTANT 〉=15, it is characterized in that described latex particle contains weight ratio and is at least 4 described at least a polyanionic compound and described polymer.
The same method for preparing conductive coating that adopts realizes each side of the present invention, described method comprises the steps: under oxidation or reducing condition, in the presence of at least a polyanionic compound, the aqueous solution or the dispersion liquid that in reaction medium, comprise the polymer that the construction unit of monomeric unit shown in the formula (I) is formed by the preparation of use initator initiated polymerization
Wherein the weight rate of at least a polyanionic compound and described construction unit is 4: 1 to 20: 1 in the course of reaction; Preparation contains described polymer and described at least a polyanionic compound and contains two or first coating composition of the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-in moisture or non-aqueous media; Thereby described first coating composition is coated to forms first coating on the object; Heat described first coating down at least 100 ℃ again.
The same method for preparing conductive coating that adopts realizes each side of the present invention, described method comprises the steps: under oxidation or reducing condition, in the presence of at least a polyanionic compound, the aqueous solution or the dispersion liquid that in reaction medium, comprise the polymer that the construction unit of monomeric unit shown in the formula (I) is formed by the preparation of use initator initiated polymerization
Figure C20048002373100122
Wherein the weight ratio of at least a polyanionic compound and described construction unit is 4: 1 to 20: 1 in the course of reaction; Preparation contains second coating composition of the aprotic compound of described polymer and described at least a polyanionic compound and DIELECTRIC CONSTANT 〉=15 in moisture or non-aqueous media; Described second coating composition is coated to formation second coating on the object; Under at least 50 ℃ temperature, heat described second coating again.
The same method for preparing electrically-conducting paint that adopts realizes each side of the present invention, described method comprises the steps: under oxidation or reducing condition, in the presence of polyanion, the aqueous solution or the dispersion liquid that in reaction medium, contain the polymer of construction unit shown in the formula (I) by the preparation of use initator initiated polymerization
Figure C20048002373100131
Wherein the molar ratio of the anion base in construction unit and the polyanion is 4: 1 to 10: 1 shown in the course of reaction Chinese style (I); Preparation contains described polymer and described polyanion and contains two or first coating composition of the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-in moisture or non-aqueous media; Described first coating composition is coated to formation first coating on the object; Under at least 100 ℃ temperature, heat described first coating again.
The same method for preparing electrically-conducting paint that adopts realizes each side of the present invention, described method comprises the steps: under oxidation or reducing condition, in the presence of polyanion, the aqueous solution or the dispersion liquid that in reaction medium, contain the polymer of construction unit shown in the formula (I) by the preparation of use initator initiated polymerization
Figure C20048002373100132
Wherein the molar ratio of the anion base of construction unit shown in the formula described in the course of reaction (I) and polyanion is 4: 1 to 10: 1; Preparation contains second coating composition of the aprotic compound of described polymer and described polyanion and DIELECTRIC CONSTANT 〉=15 in moisture or non-aqueous media; Described second coating composition is coated to formation second coating on the object; Under at least 50 ℃ temperature, heat described second coating again.
Open the preferred embodiments of the invention in detailed Description Of The Invention.
Detailed Description Of The Invention
Definition
It should be noted and also comprise the described material of a class when in specification and additional claims, mentioning certain material.Therefore, comprise that as " thiophene shown in the formula (I) " more than this a kind of class thiophene, the polymerization of " thiophene shown in the formula (I) " comprises the copolymerization more than a kind of this class thiophene.
The term polymer comprises homopolymers, copolymer, ter-polymers, graft polymers and block copolymer and chain polymer and condensation polymer.
Term C 1-5Alkylidene is represented methylene-dioxy, 1,2-ethylenedioxy, 1, the inferior third dioxy base, 1 of 3-, 4-Aden dioxy base and 1, the inferior penta dioxy base of 5-.
The term initator be meant can initiated polymerization species.
The term alkyl comprises the possible variant of the institute of each carbon number alkyl, and promptly the alkyl for three carbon atoms comprises n-pro-pyl and isopropyl; Alkyl for four carbon atom comprises normal-butyl, isobutyl group and the tert-butyl group; Alkyl for five carbon atoms comprises n-pentyl, 1,1-dimethyl-propyl group, 2,2-dimethyl propyl and 2-methyl butyl etc.
Being used for term water-bearing media of the present invention is meant and contains at least 60% volume water, the liquid of preferred at least 80% volume water, optional contain can be miscible with water organic solvent, as alcohols (as methyl alcohol, ethanol, 2-propyl alcohol, butanols, isoamyl alcohol, octanol, hexadecanol etc.), di-alcohols (as ethylene glycol), glycerol, N-methyl pyrrolidone, the pure and mild ketone of methoxy propyl (as 2-acetone and 2-butanone etc.).
Be used for term non-aqueous media of the present invention and be meant all liq that is not included in the term water-bearing media.
The term conduction is meant that sheet resistance is lower than 10 6Ω/sq.
Term " conductance raising " is meant the method that improves conductance, wherein as by the contact high boiling liquid as containing two or the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-, optional subsequently under higher temperature, preferred 100 to 250 ℃, heat and improved conductance in preferred 1 to 90 second.Perhaps under the situation of the aprotic compound of DIELECTRIC CONSTANT 〉=15 such as N-methyl pyrrolidone, adopt to be lower than 100 ℃ temperature.Can observe this conductance raising and the raising of this conductance generation or generation subsequently in the outermost layer preparation process with polythiophene.The particularly preferred liquid that is used for this processing is N-methyl pyrrolidone and diethylene glycol (DEG), described in EP-A 0686662 and EP-A 1003179.
Be used for PEDOT representative disclosed by the invention poly-(3, the 4-Ethylenedioxy Thiophene).
Be used for EDOT disclosed by the invention and represent 3, the 4-Ethylenedioxy Thiophene.
Be used for ADOT disclosed by the invention and represent 3, the 4-subalkane dioxide thiophene.
Be used for PSS representative disclosed by the invention poly-(styrene sulfonic acid) or poly-(styrene sulfonate).
Be used for PET disclosed by the invention and represent PETG.
The aqueous dispersions of latex
In first embodiment of the aqueous dispersions of latex of the present invention, the primary particle size of described latex is less than 30nm.
In second embodiment of the aqueous dispersions of latex of the present invention, the weight ratio of at least a polyanionic compound described in its preparation process and described polymer and the weight ratio of described construction unit and described at least a polyanionic compound are corresponding.
In the 3rd embodiment of the aqueous dispersions of latex of the present invention, described latex particle contains weight ratio greater than 4 and less than 20 at least a polyanionic compound and described polymer.
In the 4th embodiment of the aqueous dispersions of latex of the present invention, wherein said latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 8500mg oxygen/liter described reaction medium.
In the 5th embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 2000 milligrams of oxygen/liter described reaction medium.
In the 6th embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 1000 milligrams of oxygen/liter described reaction medium.
In the 7th embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 500 milligrams of oxygen/liter described reaction medium.
In the 8th embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 100 milligrams of oxygen/liter described reaction medium.
In the 9th embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 3 milligrams of oxygen/liter described reaction medium.
In the tenth embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 1.5 milligrams of oxygen/liter described reaction medium.
In the 11 embodiment of the aqueous dispersions of latex of the present invention, described latex prepares in reaction medium, and the oxygen concentration when adding initator in the reaction medium is less than 0.5 milligram of oxygen/liter described reaction medium.
In the 12 embodiment of the aqueous dispersions of latex of the present invention, monomeric unit shown in the formula (I) is selected from 3 of optional alkyl replacement, 3 of 4-methylendioxythiopheunits units, optional alkyl or aryl replacement, 4-Ethylenedioxy Thiophene unit, optional alkyl or aryl replace 3,4-Ethylenedioxy Thiophene unit, R wherein 1And R 2Be 1 together, 3 of unit shown in the formula of 2-cyclohexylidene (I), optional alkyl or aryl replacement, 3 of the inferior third dioxy base thiophene unit of 4-, optional alkyl or aryl replacement, 3 of 4-Aden dioxy base thiophene unit and the replacement of optional alkyl or aryl, the inferior penta dioxy base thiophene unit of 4-.
In the 13 embodiment of the aqueous dispersions of latex of the present invention, polymer be at least a under 25 ℃ the solubility in water less than 3 of 2.2g/L, 4-subalkane dioxide thiophene compound and at least a under 25 ℃ the solubility in water be at least 3 of 2.2g/L, the copolymer of 4-subalkane dioxide thiophene compound.
In the 14 embodiment of the aqueous dispersions of latex of the present invention, polymer be at least a under 25 ℃ the solubility in water less than 3 of 2.2g/L, 4-subalkane dioxide thiophene compound and at least a under 25 ℃ the solubility in water be at least 3 of 2.2g/L, the copolymer of 4-subalkane dioxide thiophene compound, and the solubility under 25 ℃ in water is at least 3 of 2.2g/L, 4-subalkane dioxide thiophene compound is selected from 3,4-dihydro-2H-thieno [3,4-b] [1,4] methyl alcohol dioxine-2-yl), 3,4-dihydro-2H-thieno [3,4-b] [1,4] two oxa-English in heptan-3-alcohol, (2,3-dihydro-thieno [3,4-b] [1,4] ethyl acetate dioxine-2-base-methoxyl group), (2,3-dihydro-thieno [3,4-b] [1,4] acetate dioxine-2-base-methoxyl group), 2-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethoxyl methyl }-2,3-dihydro-thieno [3,4-b] [1,4] dioxine and 4-(2,3-dihydro-thieno [3,4-b] [1,4] dioxine-2-ylmethoxy)-butane-1-sulfonate sodium.
Preparation contains the aqueous solution of the polymer of monomeric unit shown in the chemical formula (I) or the method for dispersion liquid
A step of the inventive method is under oxidation or reducing condition, in the presence of at least a polyanionic compound, in reaction medium, quote the aqueous solution or the dispersion liquid that polymerization prepares the polymer of being made up of the construction unit that comprises monomeric unit shown in the formula (I) by the use initator
Figure C20048002373100171
Wherein the weight ratio of at least a polyanionic compound and construction unit described in the course of reaction is 5: 1 to 20: 1.
In first embodiment of the inventive method, the mol ratio of (3, the 4-dialkoxythiophene) polymer or copolymer and at least a polyanionic compound is 1: 5 to 1: 8.0 in solution or the dispersion liquid.
In second embodiment of the inventive method, the concentration of monomeric unit in described reaction medium shown in the described formula (I) is 60mM or lower.
Oxygen concentration in the reaction medium can be regulated by any means, as freezes molten technology, prolongs inert gas such as argon, nitrogen, the bubbling time of helium in reaction medium, passes through the consumption reaction oxygen consumed under inert gas cover.
In the 3rd embodiment of the inventive method, inert gas is nitrogen, helium or argon gas.
As Journal of the American Chemical Society, 85 volumes, 454-458 page or leaf (1963) and J.Polymer Science Part A Polymer Chemistry, 26 volumes, the oxidant of the oxidation polymerization of the described pyrroles of being used for of embodiment in the 1287-1294 page or leaf (1988) can be used for the oxidation polymerization of thiophene.
In the 4th embodiment of the inventive method, oxidant chosen from Fe (III) salt such as the FeCl that are polymerized to oxidation polymerization and are used for the cheap of initiated polymerization and obtain easily 3, organic acid iron (III) salt such as Fe (OTs) 3, H 2O 2, K 2Cr 2O 7, persulfuric acid alkali metal salt and ammonium persulfate, perboric acid alkali metal salt and potassium permanganate.
In theory, the oxidation polymerization of thiophene needs the thiophene [referring to as J.Polymer Science Part A Polymer Chemistry, 26 roll up 1287-1294 page or leaf (1988)] of the oxidant/mole formula (I) of 2.25 equivalents.In practice, every polymerized unit adopts the oxidant of excessive 0.1 to 2 equivalent.Use persulfate and iron (III) salt to have significant technical advantage: they do not have corrosiveness.In addition, under the situation that special additive exists, the oxidation polymerization of thiophene shown in the formula (I) is carried out very slowly, and thiophene and oxidant can combine and become solution or slurry and be coated on the pending matrix.Be coated be covered with this solution or slurry after, as US6,001,281 and WO 00/14139 described in, come the accelerated oxidation polymerization by the heating tape coating of material, described patent is by reference in conjunction with leading herein.
Employing Appperloo etc. are at Chem.Eur.Journal, 8 volumes, the 2384-2396 page or leaf, Stille (organotin) or Suzuki (organic boron) route described in 2002 can carry out reductive polymerization, at Tetrahedron Letters, 42 volumes, the 155-157 page or leaf, in 2001 and at Macromolecules, 31 volumes, the 2047-2056 page or leaf also discloses this two kinds of routes in 1998; Or as at Bull.Chem.Soc.Japan, 72 volumes, 621 pages, 1999 and at Advanced Materials, 10 volumes, 93-116 page or leaf, the employing nickel complex described in 1998.
The polymer that contains monomeric unit shown in the formula (I) can prepare by monomeric unit shown in the chemical copolymerization formula (I) and other polymerizable heterocyclic compound (as the pyrroles) equally.
Oxygen concentration determination
Use Knick Process Unit 73 O available from Mettler Toledo 2, adopt InPro 6000 serial O 2Transducer can be measured oxygen concentration.The Clark Polarographic sensor is mainly by work electrode (negative electrode), form to electrode/reference electrode (anode) with the oxygen flow film that electrode and medium separate.Transmitter provides oxygen reduction required constant polarizing voltage for negative electrode.The oxygen molecule that sees through film is reduced at negative electrode.Separate out at the anode metal (silver) of anode generation oxidation and oxidation simultaneously and enter in the electrolyte.Electrolyte has been communicated with the circuit (ionic conductivity) between anode and the negative electrode.Oxygen (O in the sample media be measured and be proportional to the electric current of Chan Shenging can by transmitter like this 2) dividing potential drop.
Oxygen concentration is 6.5mg/L in the aqueous solution of poly-(styrene sulfonic acid) of 6% weight of measuring with this technology.
Pass through the oxygen bubbling is passed through poly-(styrene sulfonic acid) solution under 25 ℃ and 1013 millibars, and it is reached capacity, this moment, oxygen concentration was 38,45mg/L.This value can be considered under 25 ℃ and the 1013 millibars oxygen maxima solubility at poly-(styrene sulfonic acid) solution.
Contain the electrochemical polymerization of the polymer of monomeric unit shown in the formula (I)
The polymer that contains monomeric unit shown in the formula (I) can prepare by electrochemical polymerization.The electrochemically oxidative polymerization of thiophene compound carries out to the temperature of solvent for use boiling point at-78 ℃ shown in the formula (I), preferred-20 ℃ to 60 ℃ temperature.Reaction time decides according to concrete thiophene, is generally several seconds to several hours.Dietrich etc. are at Journal Electroanalytical Chemistry, 369 volumes, the 87-92 page or leaf, in 1994 the electrochemical polymerization to thiophene compound be described.
The inert fluid that is suitable in the electrochemical oxidation process of thiophene compound shown in the formula (I) is a water, alcohols (as methyl alcohol and ethanol), ketone (as acetophenone), halogenated hydrocarbon is (as carrene, chloroform, carbon tetrachloride and fluorohydrocarbon), ester class (as ethyl acetate and butyl acetate), aromatic hydrocarbons is (as benzene, toluene and dimethylbenzene), aliphatic hydrocarbon is (as pentane, hexane, heptane and cyclohexane), nitrile (as acetonitrile and benzonitrile), sulfoxide class (as methyl-sulfoxide), the sulfone class is (as dimethyl sulfone, the phenyl methyl sulfone), the liquid aliphatic amide-type is (as methylacetamide, dimethylacetylamide, dimethyl formamide, pyrrolidones, N-methyl-pyrrolidones, caprolactam, N-methyl-caprolactam), the aliphatic series and the aromatics ethers (as Anaesthetie Ether and methyl phenyl ethers anisole) of aliphatic series ethers and mixing, liquid ureas (as tetramethylurea or N, the N-dimethyl-2-imidazolidinone).
Be used for the preferred free acid of electrolysis additive or the conducting salt commonly used of the electrochemical polymerization of thiophene compound shown in the formula (I), it shows the certain dissolubility energy in solvent for use.Particularly suitable electrolyte is the combination of alkali metal, alkaline-earth metal or optional alkylation An, Phosphonium, sulfonium or oxygen cation and perchlorate, tosylate, tetrafluoroborate or Liu Fu Phosphonium acid radical anion.
The use amount of electrolysis additive makes and produce the electric current of 0.1mA at least in electrochemical oxidation process.
Electrochemical polymerization can be carried out continuously or intermittently.Well-known electrode material is the glass, noble metal or the wire netting that cover of ITO, insulating barrier and the carbon felt that fills carbon polymer, band steam metal coating.
Current density in the electrochemical oxidation process can change in relative broad range.Current density in the 8th embodiment of the present invention is 0.0001 to 100mA/cm 2Current density in the 9th embodiment of the present invention is 0.01 to 40mA/cm 2The voltage of negative electrode is set at 0.1 to 50V under these current densities.
The polymer that contains monomeric unit shown in the formula (I) also can prepare by monomeric unit shown in the electrochemistry copolymerization formula (I) and other polymerizable heterocyclic compound (as the pyrroles).
Polyanionic compound
The polyanionic compound that is used for dispersion liquid of the present invention is open and comprise that the carboxylic acid of polymerization such as polyacrylic acid, polymethylacrylic acid, poly and poly-sulfonic acid are as poly-(styrene sulfonic acid) at EP-A 440957.These polycarboxylic acids and poly-sulfonic acid is vinyl carboxylic acid and vinyl sulfuric acid and other polymerisable monomer such as acrylate, methacrylate and cinnamic copolymer also.
In the 16 embodiment of the aqueous dispersions of latex of the present invention, described at least one kind polyanionic compound comprises polystyrolsulfon acid.
Industrial applicability
The polymer that contains monomeric unit shown in the formula (I) of chemistry or electrochemical preparation demonstrates high conductance, low visible absorption and high infrared radiation and absorbs.Therefore its each layer has high conductivity, high transparent and heat insulation to visible light.This polythiophene can be used for multiple firm and soft matrix as pottery, glass and plastics.Be particularly suitable for soft matrix such as plastic sheet, these matrixes can be done than macrobending and distortion and the not loss of the conductance of polythiophene layer.
Therefore this polythiophene can be used for optoelectronic device, battery, capacitor and organic, inorganic EL equipment, electro-magnetic screen layer, thermal insulation layer, comprise photographic film, the antistatic coating of multiple products such as thermal imaging recording materials and photothermographic recording materials, smart window (smartwindow), electrochromic device, organic and biological organic material transducer, field-effect transistor, printed panel, conductive adhesive resin and stand alone type (free-standing) conductive film is [equally referring to Handbook of Oligo-and Polythiophenes, the 10th chapter, D.Fichou edits, Wiley-VCH, Weinheim (1999)].
Below the present invention will be described by comparative example and the embodiment of the invention.Unless otherwise indicated, otherwise percentage that provides among the embodiment and ratio calculate by weight.
Coating Nr.01 composed as follows that is used for each embodiment:
Figure C20048002373100211
3,4-subalkane dioxide thiophene-polymer manufacture
Embodiment 1
Under 25 ℃, poly-(styrene sulfonic acid) [PSS] (Mw=290,000) solution of listing in the amount in the table 2 is mixed in the appropriate reaction container of belt stirrer and nitrogen inlet with the deionized water of listing in the amount of each the concrete PEDOT type of correspondence in the table 2.Nitrogen bubble was passed through mixture after 30 minutes, and the EDOT that will list in the amount of each the concrete PEDOT type of correspondence in the table 2 again adds in this solution.With Knick Process Unit 73 O 2, adopt InPro 6000 serial O 2Oxygen concentration in the solution of measuring is listed in the table 2.Add consumption then respectively with 0.13 and the corresponding Fe of 41.6mM concentration 2(SO 4) 39H 2O and Na 2S 2O 8Come initiated polymerization.The concentration of EDOT in the reactant mixture is 30mM and the concentration of PSS is 57mM.Stirred the mixture 7 hours in 25 ℃ again, add the Na of the consumption corresponding of corresponding each concrete PEDOT type subsequently again with 6.95mM concentration 2S 2O 8After reacting 16 hours again, with ion-exchanger (300mL Lewatit TMS100MB+500mL Lewatit TMM600MB) reaction mixture is twice.The mixture that obtains is handled the cementitious mixtures that obtains again in 95 ℃ of following heat treatments 2 hours and with high shear [high pressure microjet nano-dispersed instrument (microfluidizer) is under 60MPa (600Bar)].
Table 2
Figure C20048002373100221
*The PSS aqueous solution of 4.93% weight
The PSS aqueous solution of #4.68% weight
Employing prepares the conductive layer of Class1 based on the dispersion liquid of the dispersion liquid among the embodiment 1
Add 3-glycidoxy propyl group-trimethoxy silane,
Figure C20048002373100231
FSO100, the copolymer emulsion and the N-methyl-pyrrolidones of the inferior ethene of dichloro, methacrylate and itaconic acid (88/10/2) obtain coating dispersing liquid in the dispersion liquid of embodiment 1, with the coatings that scraper plate is coated on the 175 μ m PETG supporters and drying made Class1 in 3.5 minutes under 45 ℃, composed as follows:
Figure C20048002373100232
To the sign of employing based on the conductive layer of the dispersion liquid preparation of the dispersion liquid among the embodiment 1
With the band visible filter
Figure C20048002373100233
The TD904 opacimeter is measured one of 10 compositions and is folded the optical density that sample is determined multilayer, obtains the optical density of monolithic more thus.Data in the table 3 comprise the optical density of PET-supporter.
In temperature is that 25 ℃, relative humidity are the sheet resistance that layer that 30% the indoor parallel copper electrode that can form the line contact (every long 35mm and at a distance of 35mm) contact has coated is measured each layer, uses
Figure C20048002373100234
Insulator separates electrode.This can realize the direct measurement of sheet resistance.The result who obtains also is summarised in the table 3.
Table 3
The PEDOT type The amount of PEDOT/PSS dispersion liquid [g] O in the reaction medium 2Amount [mg/L] PEDOT/PSS concentration [% weight] Initial surface resistance [Ω/sq] The optical density of band PET supporter
1 90,000 0.080 0.82 1500
2 95,844 0.995 0.77 2010
3 91,111 0.995 0.81 1830
4 1800 6.5 1.09 2900 0.067
5 1535 8.36 0.82 4120
6 1760 38.45 1.11 21000 0.066
Result in the table 3 shows: PSS: the PEDOT mol ratio is that the sheet resistance of 1.90 PEDOT/PSS layer significantly improves along with the raising of oxygen concentration in the reaction medium.
Embodiment 2
Under 25 ℃, poly-(styrene sulfonic acid) [PSS] (Mw=290,000) solution of listing in the amount in the table 4 is mixed in the appropriate reaction container of belt stirrer and nitrogen inlet with the deionized water of listing in the amount of each the concrete PEDOT type of correspondence in the table 4.Nitrogen bubble was passed through mixture after 30 minutes, and the EDOT that will list in the amount of each the concrete PEDOT type of correspondence in the table 4 again adds in the described solution.Oxygen concentration＜1.0mg/L in the solution is with Knick Process Unit 73O 2, adopt InPro 6000 serial O 2Measure.Add consumption then respectively with 0.13 and the corresponding Fe of 41.6mM concentration 2(SO 4) 39H 2O and Na 2S 2O 8Come initiated polymerization.The concentration of EDOT in the reactant mixture is 30mM and the concentration of PSS is 57mM.Stirred the mixture 7 hours in 25 ℃ again, add the Na of the consumption corresponding of corresponding each concrete PEDOT type subsequently again with 6.95mM concentration 2S 2O 8After reacting 16 hours again, with ion-exchanger (300mL Lewatit TMS100MB+500mLLewatit TMM600MB) reaction mixture is twice.The mixture that obtains is handled the cementitious mixtures that obtains again in 95 ℃ of following heat treatments 2 hours and with high shear [high pressure microjet nano-dispersed instrument is under 60MPa (600Bar)].
Table 4
Figure C20048002373100251
Preparation and sign based on the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid of embodiment 2
As described in the dispersion liquid of embodiment 1, prepare the conductive layer of Class1 and it is characterized based on the dispersion liquid of the dispersion liquid of embodiment 2.The result is summarised in the table 5.
Table 5
The PEDOT type The amount of PEDOT/PSS dispersion liquid [g] PEDOT/PSS concentration [% weight] Sheet resistance [Ω/sq] Optical density
1 1950 1.02 1200 0.066
2 1840 1.03 1200 0.065
The result of associative list 3 and table 5 shows: the initial surface resistance of PEDOT/PSS layer depends in the presence of poly-(styrene sulfonic acid) 3 strongly, the amount of the oxygen in the reaction medium in the 4-Ethylenedioxy Thiophene polymerization process.Oxygen concentration is low more in the reaction medium, and sheet resistance is low more.
Embodiment 3
Under 25 ℃, poly-(styrene sulfonic acid) [PSS] (Mw=290,000) solution of listing in the amount in the table 6 is mixed in the appropriate reaction container of belt stirrer and nitrogen inlet with the deionized water of listing in the consumption of each the concrete PEDOT type of correspondence in the table 6.Nitrogen bubble was passed through mixture after 30 minutes, and the EDOT that will list in the consumption of each the concrete PEDOT type of correspondence in the table 7 again adds in the described solution, and obtaining EDOT concentration is 30mM.Oxygen concentration＜1.0mg/L in the solution is with Knick Process Unit 73 O 2, adopt InPro 6000 serial O 2Measure.The Fe that adds corresponding with 0.13 and 41.6mM concentration respectively consumption then 2(SO 4) 39H 2O and Na 2S 2O 8Come initiated polymerization.The concentration of EDOT in the reactant mixture is 30mM, and each concrete PEDOT type in the PSS concentration correspondence table 6.
Table 6
Figure C20048002373100261
*Except not 95 ℃ of following heat treatments 2 hours, other condition is identical with PEDO1 Class1 7.
The PSS aqueous solution of #4.90% weight
*The PSS aqueous solution of 4.93% weight
Stirred the mixture 7 hours in 25 ℃ again, add the Na of the consumption corresponding of corresponding each concrete PEDOT type subsequently again with 6.95mM concentration 2S 2O 8After reacting 16 hours again, with ion-exchanger (300mL Lewatit TMS100MB+500mL Lewatit TMM600MB) reaction mixture is twice.The mixture that obtains is handled the cementitious mixtures that obtains again in 95 ℃ of following heat treatments 2 hours and with high shear [high pressure microjet nano-dispersed instrument is under 60MPa (600Bar)].
Gained PSS: PEDOT weight ratio and mol ratio, PEDOT/PSS concentration, in 25 ℃ constant temperature bath, list in the table 7 greater than the numbers of particles of 1 μ m with particle diameter in the viscosity of Ubbelohde viscometer determining, the particle diameter peak value, every milliliter in the bimodal distribution of sizes.
Table 7
The PEDOT type The PSS/PEDOT weight ratio The PSS/PEDOT mol ratio PEDOT/PSS concentration [% weight] Viscosity cP Back particle diameter peak value [nm] homogenizes The # particle diameter is greater than numbers of particles/mL of 1 μ m
9 0.98 0.76 0.73 226 47 4.7×10 6
10 0.98 0.76 0.65 120 45 1.6×10 7
11 1.55 1.20 0.86 225 44 1.7×10 7
12 1.55 1.20 0.82 150 42 2×10 7
13 1.98 1.53 0.81 45 31 8.3×10 6
14 2.46 1.90 - 56 25 7.6×10 6
15 2.46 1.90 - 24 - -
16 2.46 1.90 - 28 - -
17 3.18 2.45 1 64 33 3.6×10 7
18 3.18 2.45 0.93 60 32 3.2×10 7
19 6.36 4.91 1.83 94 27 2.9×10 7
20 6.36 4.91 1.89 118 26 3.3×10 7
21 6.42(50L) 4.96 1.55 59 26 1.1×10 6
22 6.42(50L-UT) 4.96 1.66 53 23 1.2×10 6
23 There is not heat treatment 4.96 1.32 59 18 1.5×10 6
Adopting the aqueous gel permeation chromatography, (is the peak area A of 254nm place with the relative quantity of UV-vis absorption detecting PSS (combination or not combination) 254) and the relative quantity of the PEDOT of combination (unconjugated can not pass through chromatographic column, do not detect PEDOT) (be the peak area A of 785nm place 785).A 254/ A 785Provided the relative molecular weight of PSS with the PEDOT that combines.In order to obtain representative result, need be under 60MPa (600bar) before carrying out GPC dispersion liquid be carried out high pressure microjet nanometer.If do not carry out high pressure microjet nanometer, because the latex of agglomeration can not pass through chromatographic column, the PEDOT summit is very little.Having determined the molecular weight of PEDOT simultaneously, is that reference material is measured with poly-(styrene sulfonic acid) sodium.The result is summarised in the table 8.
The ratio of measuring the PSS/PEDOT that obtains from GPC is obviously corresponding with in esse mol ratio, thereby shows that PSS is attached on the PEDOT basically.
Table 8
The PEDOT type The PSS/PEDOT weight ratio The PSS/PEDOT mol ratio PEDOTM n PEDOT Mw A 254 A 785 The relative mol ratio A of PSS/PEDO 254/A 785
9 0.98 0.76 1.2×10 5 2.9×10 5 0.0019 0.0008 2.38
11 1.55 1.20 4.5×10 5 7.2×10 5 0.0032 0.0013 2.46
12 1.55 1.20 4.4×10 5 7.6×10 5 0.0031 0.0014 2.21
13 1.98 1.53 2.0×10 5 4.9×10 5 0.0049 0.0031 1.58
17 3.18 2.45 2.8×10 5 7.9×10 5 0.0073 0.0025 2.92
18 3.18 2.45 3.0×10 5 8.9×10 5 0.0066 0.0024 2.75
19 6.36 4.91 4.9×10 5 9.5×10 5 0.0156 0.0029 5.38
20 6.36 4.91 4.9×10 5 9.1×10 5 0.0161 0.0023 7.0
Employing is based on the preparation and the sign of the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid of embodiment 3
Preparation is based on the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid of embodiment 3, wherein
Figure C20048002373100281
The amount of FSO 100,3-glycidoxy propyl group-trimethoxy silane, copolymer emulsion and N-methyl pyrrolidone keeps constant and quantitative changeization latex obtains constant PEDOT coverage rate [28.9mg/m 2].As described in the dispersion liquid of embodiment 1, these layers are characterized and the results are shown in the table 9.
Result in the table 9 shows unexpectedly: the sheet resistance of the layer that is contained in the PEDOT/PSS that makes under the basic oxygen-free of the present invention is along with PSS: the increase of PEDOT ratio and reducing.This is not inconsistent with data in the relevant PEDOT/PSS document, and document shows that sheet resistance is along with PSS: the increase of PEDOT ratio and increasing, referring to as above-mentioned M.Lefebvre etc. at Chem.Mater., 11 volumes, 262-268 page or leaf, the paper of delivering in 1999.
Table 9
The PEDOT type Total coverage rate [mg/m of layer 2] The % weight of PEDOT in the layer The PSSA/PEDOT weight ratio Sheet resistance [Ω/sq] The optical density that does not have the PET supporter The optical density of band PET supporter
9 265.5 10.9 0.99 3000 - 0.061
10 265.5 10.9 0.99 3300；3680 0.028 0.062
11 282.3 10.2 1.57 1700 - 0.065
12 282.3 10.2 1.57 1600；1710 0.031 0.065
13 294.1 9.8 1.98 1800 - -
14 308 9.4 2.46 1500；2010 0.027 -
15 308 9.4 2.46 2010 0.028 -
16 308 9.4 2.46 1830 0.028 -
17 329.7 8.8 3.21 870；1000 0.028 0.063
18 329.7 8.8 3.21 770 - 0.065
19 422.4 6.8 6.42 730 - 0.064
20 422.4 6.8 6.42 720 - 0.065
21 422.4 6.8 6.42(50L) 640 - 0.066
22 422.4 6.8 6.42(50L-UT) 640 - 0.065
23 422.4 6.8 6.42 there is not heat treatment 690 - 0.067
Employing prepares the conductive layer of type 2 based on the dispersion liquid of the dispersion liquid of embodiment 3
Add 3-glycidoxy propyl group-trimethoxy silane, ZONYL TmFSO100, diethylene glycol (DEG) make coating dispersing liquid in the PEDOT/PSS dispersion liquid, be coated to again to produce on the PETG supporter that applies with coating 1 to cover, then 140 ℃ dry 1 minute down, described coating is composed as follows:
PEDOT/PSS Number change is to keep the constant coverage rate 20.2mg/m of PEDOT 2
3-glycidoxy propyl group-trimethoxy silane 24mg/m 2
ZONYL TMFSO100 11mg/m 2
Diethylene glycol (DEG) [DEG] (theoretical value) 1.33mg/m 2
Sign based on the conductive layer of the type 2 of the dispersion liquid preparation of the dispersion liquid of embodiment 3
As above described optical density and the sheet resistance of measuring layer of the conductive layer of Class1.The result is summarised in table 10.
Table 10
The PEDOT type Total coverage rate [mg/m of layer 2] The % weight of PEDOT in the layer The PSSA/PEDOT weight ratio The PSSA/PEDOT mol ratio Sheet resistance [Ω/sq] The optical density that does not have supporter
10 75.2 26.9 0.99 0.76 1340 0.017
12 86.9 23.2 1.57 1.21 869 0.016
14 105 19.2 2.46 1.90 736 0.012
15 105 19.2 2.46 1.90 794 0.013
16 105 19.2 2.46 1.90 754 0.013
17 120.0 16.8 3.21 2.48 640 0.013
20 184.9 10.9 6.42 4.96 520 0.013
Result in the table 10 unexpectedly shows in addition: the sheet resistance of the layer that is contained in the PEDOT/PSS that makes under the basic oxygen-free of the present invention is along with PSS: the increase of PEDOT ratio and reducing.This is not inconsistent with data in the relevant PEDOT/PSS document, and document shows that sheet resistance is along with PSS: the increase of PEDOT ratio and increasing, referring to as above-mentioned M.Lefebvre etc. at Chem.Mater., 11 volumes, 262-268 page or leaf, the paper of delivering in 1999.
Determining of actual PSS/PEDOT ratio
Under high vacuum (0.7mbar), in CHRIST BETA 2-16 dividing plate freeze dryer (shelffreeze-dryer),, be evaporated (promptly equaling room temperature) and obtain dry powder up to baffle temperature up to all water with the PEEDOT dispersion liquid sample freeze drying of Class1 0,13,17 and 19/20.
Usefulness is with the 200MHz spectrometer then 13C CP/MAS under time of contact is that 6.4kHz analyzes the obtained freeze-drying sample with the velocity of rotation at 11 different Milliseconds, and each the measurement repeated 3000 times to improve signal to noise ratio.Whole procedure such as P.Adriaensens etc. are at Polymer, and 43 roll up, the 7003-7006 page or leaf, and described in 2002, each sample carried out 30 hours.The C-displacement of EDOT ring (68ppm) separates fully with near aliphatic PSS signal (40ppm).According to relational expression:
Ln (carbon intensity)=ln (initial carbon intensity)-t/T 1pH
Analyze 1n (carbon intensity) and determine PSS: the quantitative mol ratio of PEDOT with the correlated characteristic of time of contact (CT) and with the initial carbon intensity that obtains thus.The T of each signal 1pH difference slack time, the slack time of each sample is also different equally.Quantitative results needs so long mensuration program.The T of the PEDOT ether of aromatics PSS carbon atom, aliphatic PSS carbon atom, every kind of PEDOT-type 1pH lists in the following table 11 slack time.
Table 11
The PEDOT type The T of PSS aromatic carbon atom 1pH[ms] The T of PSS aliphatic carbon atom 1pH[ms] The T of PEDO ether carbon atom 1pH[ms]
13 3.6 2.3 2.8
17 4.4 3.1 2.9
19/20 2.8 1.9 1.9
10 1.6 1.0 1.1
The average initial carbon atom intensity of the average initial carbon atom intensity of the initial aromatic carbon atom intensity of the PSS that obtains thus, the initial aliphatic carbon atom intensity of PSS, PSS, the initial ether carbon atom intensity of PEDOT, PSS is listed in the table 12 with the theoretical molar of the PSS/PEDOT when ratio of the initial ether carbon atom intensity of PEDOT.
The theoretical molar of PSS/PEDOT has proved the validity of method therefor than very consistent with actual mol ratio.Therefore, from 13C CP/MAS analyzes the mol ratio obtain and theoretical molar than in full accord.
Table 12
The PEDOT type The PSS/PEDOT mol ratio (theoretical) The initial aromatic carbon atom intensity of PSS The initial aliphatic carbon atom intensity of PSS The average initial carbon atom intensity of PSS The initial ether carbon atom intensity of PEDOT The initial ether carbon atom intensity of average initial carbon atom intensity/PEDOT of PSS
13 1.55 232 223 228 155 1.47
17 2.45 421 415 418 160 2.61
19/20 4.91 343 335 339 66 5.14
10 0.76 73 47 60 73 0.82
Embodiment 4
Under 25 ℃, list in poly-(styrene sulfonic acid) [PSS] (Mn=160 of the amount in the table 13,000 and Mw=600,000) solution and the deionized water of listing in the consumption of each the concrete PEDOT type of correspondence in the table 13 mix in the appropriate reaction container of belt stirrer and nitrogen inlet.Nitrogen bubble was passed through mixture after 30 minutes, and the EDOT that will list in the consumption of each the concrete PEDOT type of correspondence in the table 13 again adds in the described solution.Oxygen concentration＜1.0mg/L in the solution is with Knick Process Unit 73 O 2, adopt InPro 6000 serial O 2Measure.The Fe that adds corresponding with 0.13 and 41.6mM concentration respectively consumption then 2(SO 4) 39H 2O and Na 2S 2O 8Come initiated polymerization.The concentration of EDOT in the reactant mixture is that the concentration of the PSS of 30mM and PEDOT type 24 is that the concentration of the PSS of 46mM, PEDOT type 25 is that the concentration of the PSS of 37mM, PEDOT type 26 is that the concentration of the PSS of 57mM, PEDOT type 27 is that the concentration of the PSS of 69mM, PEDOT type 28 is 93mM.Stirred the mixture 7 hours in 25 ℃ again, add the amount Na corresponding of corresponding each concrete PEDOT type subsequently again with 6.94mM concentration 2S 2O 8After reacting 16 hours again, with ion-exchanger (300mL Lewatit TMS100MB+500mL Lewatit TMM600MB) reaction mixture is twice.The mixture that obtains is handled the cementitious mixtures that obtains again in 95 ℃ of following heat treatments 2 hours and with high shear [high pressure microjet nano-dispersed instrument is under 60MPa (600Bar)].
Table 13
Figure C20048002373100331
Gained PSS: PEDOT weight ratio and mol ratio, PEDOT/PSS concentration, in 25 ℃ constant temperature bath, list in the table 14 greater than the numbers of particles of 1 μ m with particle diameter in the viscosity of Ubbelohde viscometer determining, the particle diameter peak value, every milliliter in the bimodal distribution of sizes.
Table 14
The PEDOT type The PSS/PEDOT weight ratio The PSS/PEDOT mol ratio PEDOT/PSS concentration [% weight] Viscosity [cP] Back particle diameter peak value [nm] homogenizes The # particle diameter is greater than numbers of particles/mL of 1 μ m
24 2.00 1.54 0.93 240 67 8.2×10 5
25 2.46 1.90 1.21 10 101 7.9×10 5
26 2.46 1.90 1.22 50 98 7.2×10 5
27 3.00 2.32 1.35 31 87 8.0×10 5
28 4.00 3.09 1.75 57 83 8.4×10 5
Employing is based on the preparation and the sign of the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid among the embodiment 4
Preparation is adopted based on the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid of embodiment 4 and as described in the dispersion liquid of embodiment 3 it is characterized.The result of Class1 conductive layer is summarised in the table 15.
Table 15
The PEDOT type Total coverage rate [mg/m of layer 2] The % weight of PEDOT in the layer The PSSA/PEDOT weight ratio The PSSA/PEDOT mol ratio Sheet resistance [Ω/sq] The optical density that has supporter
24 294.7 9.8 2.00 1.54 3300 0.059
25 308 9.4 2.46 1.90 1900 0.063
26 308 9.4 2.46 1.90 1700 0.063
27 323.6 8.9 3.00 2.32 1500 0.062
28 352.5 8.2 4.00 3.09 1300 0.062
Result verification in the table 15 result in the table 9, unexpectedly show in addition: the sheet resistance of the layer that is contained in the PEDOT/PSS that makes under the basic oxygen-free of the present invention is along with PSS: the increase of PEDOT ratio and reducing.
Inventive embodiments 5
Under 25 ℃, poly-(styrene sulfonic acid) [PSS] that lists in the amount in the table 13 (originated from the VERSA TL77 of ALCO, Mn=25,000, Mw=72,000) solution and enough deionized waters mix in belt stirrer appropriate reaction container and obtain 2000g solution, and the consumption of each concrete PEDOT type of correspondence is referring to table 16.The EDOT that will list in the consumption of each the concrete PEDOT type of correspondence in the table 15 again adds in the described solution, and obtaining EDOT concentration is 30Mm.With Knick Process Unit 73 O 2, adopt InPro 6000 serial O 2Measure the oxygen concentration in the solution.The Fe that adds corresponding with 0.13 and 41.6mM concentration respectively consumption then 2(SO 4) 39H 2O and Na 2S 2O 8Come initiated polymerization.The concentration of EDOT in the reactant mixture is 30mM, and the ultimate density of the PSS of corresponding each concrete PEDOT type is listed in the table 16 in the reactant mixture.Stirred the mixture 7 hours in 25 ℃ again, add the Na of the consumption corresponding of corresponding each concrete PEDOT type subsequently again with concentration 6.94mM 2S 2O 8After reacting 16 hours again, with ion-exchanger (300mL Lewatit TMS10OMB+500mL Lewatit TMM60OMB) reaction mixture is twice.The mixture that obtains is handled the cementitious mixtures that obtains again in 95 ℃ of following heat treatments 2 hours and with high shear [high pressure microjet nano-dispersed instrument is under 60MPa (600Bar)].
Table 16
Figure C20048002373100351
The molecular weight of PEDOT in the use gel permeation chromatography PEDOT dispersion liquid type 26 to 30 as described in example 3 above, the results are shown in Table 17.
Table 17
The PEDOT type The PSS/PEDPT weight ratio [theoretical] The PSS/PEDOT mol ratio [theoretical] Mw Viscosity [cP] Back particle diameter peak value [nm] homogenizes
29 1.23 0.95 4.8×10 5 14 32
30 1.96 1.51 6.7×10 5 17.5 30
31 2.46 1.90 7.0×10 5 22.5 26
32 4.0 3.09 7.2×10 5 55 26
33 8.0 6.17 9.2×10 5 125 29
Preparation and sign based on the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid of embodiment 5
Characterize based on the conductive layer of the Class1 of the dispersion liquid of the dispersion liquid of embodiment 5 and to it as preparation as described in the dispersion liquid of embodiment 3.The result of the conductive layer of Class1 is summarised in the table 18.
Table 18
The PEDOT type Total coverage rate [mg/m2] of layer The % weight of PEDOT in the layer PSSA/PED OT weight ratio The PSSA/PEDOT mol ratio Sheet resistance [Ω/sq] The optical density that does not have supporter
29 272.4 10.6 1.23 0.95 9710 0.029
30 293.5 9.8 1.96 1.51 4240 0.029
31 308 9.4 2.46 1.90 4120 0.028
32 352.5 8.2 4.0 3.09 3650 0.024
33 468.1 6.2 8.0 6.17 2280 0.026
Result in the table 18 unexpectedly shows in addition: though the PEDOT/PSS dispersion liquid that in the reaction medium of certain oxygen concentration, prepares, of the present invention be contained in preparation PEDOT/PSS basic oxygen-free under layer sheet resistance along with PSS: the increase of PEDOT ratio and reducing.This is not inconsistent with data in the relevant PEDOT/PSS document, and document shows that sheet resistance is along with PSS: the increase of PEDOT ratio and increasing, referring to as above-mentioned M.Lefebvre etc. at Chem.Mater., 11 volumes, 262-268 page or leaf, the paper of delivering in 1999.
Preparation and sign based on the conductive layer of the type 2 of the dispersion liquid of the dispersion liquid of embodiment 5
Characterize based on the conductive layer of the type 2 of the dispersion liquid of the dispersion liquid of embodiment 5 and to it as preparation as described in the dispersion liquid of embodiment 3.The result of the conductive layer of Class1 is summarised in the table 19.
Table 19
The PEDOT type Total coverage rate [mg/m2] of layer The % weight of PEDOT in the layer The PSSA/PEDOT weight ratio The PSSA/PEDOT mol ratio Sheet resistance [Ω/sq] The optical density that does not have supporter
29 80.0 25.3 1.23 0.95 2850 0.017
30 94.8 21.3 1.96 1.51 1880 0.014
31 105 19.2 2.46 1.90 1930 0.013
32 136.0 14.9 4.0 3.09 1610 0.010
33 216.8 9.3 8.0 6.17 1070 0.013
Result in the table 19 unexpectedly shows in addition: even for the PEDOT/PSS dispersion liquid that in the reaction medium of certain oxygen concentration, prepares, of the present invention be contained in preparation PEDOT/PSS basic oxygen-free under layer sheet resistance along with PSS: the increase of PEDOT ratio and reducing.This is not inconsistent with data in the relevant PEDOT/PSS document, and document shows that sheet resistance is along with PSS: the increase of PEDOT ratio and increasing, referring to as above-mentioned M.Lefebvre etc. at Chem.Mater., 11 volumes, 262-268 page or leaf, the paper of delivering in 1999.
The present invention can be included in this hint or directly disclosed all features or its combination or can be by its all generality features of inferring, and no matter whether it relates to the application's invention required for protection.According to the description of front, obviously can make various modifications within the scope of the present invention to those skilled in the art.

Claims (19)

1. the aqueous dispersions of a latex particle, described latex particle contains polymer and at least a polyanionic compound of being made up of the construction unit that comprises monomeric unit shown in the formula (I),
Figure C2004800237310002C1
R wherein 1And R 2Independent separately expression hydrogen or C 1-5Alkyl or form the optional C that replaces together 1-5Alkylidene, the primary particle size of described latex particle is less than 40nm, described dispersion liquid contains with two or the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-or the aprotic compound of DIELECTRIC CONSTANT 〉=15, it is characterized in that described latex particle contains weight ratio and is at least 4 described at least a polyanionic compound and described polymer.
2. the aqueous dispersions of the latex particle of claim 1, the weight ratio of wherein said at least a polyanionic compound and described polymer is corresponding in the weight ratio of at least a polyanionic compound described in the preparation process with the monomer of forming described polymer.
3. the aqueous dispersions of claim 1 or 2 latex particle, described latex particle contain weight ratio greater than 4 and less than 20 described at least a polyanionic compound and described polymer.
4. the aqueous dispersions of the latex particle of claim 1, wherein said latex particle prepares in reaction medium, and the oxygen concentration when adding initator in the described reaction medium is less than the described reaction medium of 8.36mg oxygen/L.
5. the aqueous dispersions of the latex particle of claim 1, wherein said latex particle prepares in reaction medium, and the oxygen concentration when adding initator in the described reaction medium is less than the described reaction medium of 3mg oxygen/L.
6. the aqueous dispersions of the latex particle of claim 1, wherein said latex particle prepares in reaction medium, and the oxygen concentration when adding initator in the described reaction medium is less than the described reaction medium of 1.5mg oxygen/L.
7. the aqueous dispersions of the latex particle of claim 1, monomeric unit shown in the wherein said formula (I) be selected from that optional alkyl replaces 3,4-methylendioxythiopheunits units, optional alkyl or aryl replace 3,4-Ethylenedioxy Thiophene unit, R wherein 1And R 2Combine is 1,3 of unit shown in the formula of 2-cyclohexylidene (I), optional alkyl or aryl replacement, 3 of the inferior third dioxy base thiophene unit of 4-, optional alkyl or aryl replacement, 3 of 4-Aden dioxy base thiophene unit and the replacement of optional alkyl or aryl, the inferior penta dioxy base thiophene unit of 4-.
8. the aqueous dispersions of the latex particle of claim 1, wherein said polymer be under 25 ℃ in water solubility less than 3 of 2.2g/L, under 4-subalkane dioxide thiophene compound and 25 ℃ in water solubility be at least 3 of 2.2g/L, the copolymer of 4-subalkane dioxide thiophene compound.
9. the aqueous dispersions of the latex particle of claim 8, wherein said under 25 ℃ the solubility in water be at least 3 of 2.2g/L, 4-subalkane dioxide thiophene compound is selected from (3,4-dihydro-2H-thieno [3,4-b] [1,4] dioxine-2-yl) methyl alcohol, 3,4-dihydro-2H-thieno [3,4-b] [1,4] two oxa-English in heptan-3-alcohol, (2,3-dihydro-thieno [3,4-b] [1,4] ethyl acetate dioxine-2-base-methoxyl group), (2,3-dihydro-thieno [3,4-b] [1,4] dioxine-2-base-methoxyl group) acetate, 2-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethoxyl methyl }-2,3-dihydro-thieno [3,4-b] and [1,4] dioxine and 4-(2,3-dihydro-thieno [3,4-b] [1,4] dioxine-2-ylmethoxy)-butane-1-sulfonate sodium.
10. the aqueous dispersions of each latex in the claim 1,2,4,5,6,7,8 and 9, wherein said at least a polyanionic compound comprises poly-(styrene sulfonic acid).
11. method for preparing conductive coating, described method comprises the steps: under oxidation or reducing condition, in the presence of at least a polyanionic compound, in reaction medium, pass through to use the initator initiated polymerization, preparation has the aqueous solution or the dispersion liquid of the polymer of structure described in the claim 1, and wherein the weight rate of at least a polyanionic compound and described construction unit described in the course of reaction is 4: 1 to 20: 1; Preparation contains described polymer and described at least a polyanionic compound and contains two or first coating composition of the organic compound of polyhydroxy and/or carboxyl or acylamino-or interior acylamino-in moisture or non-aqueous media; Described first coating composition is coated to formation first coating on the object; Heat described first coating down at least 100 ℃ again.
12. method for preparing conductive coating, described method comprises the steps: under oxidation or reducing condition, in the presence of at least a polyanionic compound, in reaction medium, pass through to use the initator initiated polymerization, preparation has the aqueous solution or the dispersion liquid of the polymer of structure described in the claim 1, and wherein the weight ratio of at least a polyanionic compound and described construction unit described in the course of reaction is 4: 1 to 20: 1; Preparation contains second coating composition of the aprotic compound of described polymer and described at least a polyanionic compound and DIELECTRIC CONSTANT 〉=15 in moisture or non-aqueous media; Described second coating composition is coated to formation second coating on the object; Under at least 50 ℃ temperature, heat described second coating again.
13. the method for claim 11 or 12, wherein when described preparation is carried out in inert gas, then when adding described initator the oxygen concentration in the reaction medium less than the described reaction medium of 8.36mg oxygen/L.
14. the method for claim 11 or 12, wherein when adding described initator, the oxygen concentration in the described reaction medium is less than the described reaction medium of 3mg oxygen/L.
15. the method for claim 11 or 12, wherein when adding described initator, the oxygen concentration in the described reaction medium is less than the described reaction medium of 1.5mg oxygen/L.
16. the method for claim 11 or 12, monomeric unit shown in the wherein said formula (I) be selected from that optional alkyl replaces 3,4-methylendioxythiopheunits units, optional alkyl or aryl replace 3,4-Ethylenedioxy Thiophene unit, R wherein 1And R 2Combine is 1,3 of unit shown in the formula of 2-cyclohexylidene (I), optional alkyl or aryl replacement, 3 of the inferior third dioxy base thiophene unit of 4-, optional alkyl or aryl replacement, 3 of 4-Aden dioxy base thiophene unit and the replacement of optional alkyl or aryl, the inferior penta dioxy base thiophene unit of 4-.
17. the method for claim 11 or 12, wherein said polymer be under 25 ℃ in water solubility less than 3 of 2.2g/L, under 4-subalkane dioxide thiophene compound and 25 ℃ in water solubility be at least 3 of 2.2g/L, the copolymer of 4-subalkane dioxide thiophene compound.
18. the method for claim 17, wherein said under 25 ℃ the solubility in water be at least 3 of 2.2g/L, 4-alkylenedioxy group thiophene compound is selected from (3,4-dihydro-2H-thieno [3,4-b] [1,4] dioxine-2-yl) methyl alcohol, 3,4-dihydro-2H-thieno [3,4-b] [1,4] two oxa-English in heptan-3-alcohol, (2,3-dihydro-thieno [3,4-b] [1,4] ethyl acetate dioxine-2-base-methoxyl group), (2,3-dihydro-thieno [3,4-b] [1,4] dioxine-2-base-methoxyl group) acetate, 2-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethoxyl methyl }-2,3-dihydro-thieno [3,4-b] and [1,4] dioxine and 4-(2,3-dihydro-thieno [3,4-b] [1,4] dioxine-2-ylmethoxy)-butane-1-sodium sulfonate.
19. the method for claim 11 or 12, wherein said at least a polyanionic compound comprises poly-(styrene sulfonic acid).
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