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WO2007066353A2 - Nouveaux polymeres de derives 3,4-propylenedioxythiophene ayant des groupes fonctionnels lateraux - Google Patents

Nouveaux polymeres de derives 3,4-propylenedioxythiophene ayant des groupes fonctionnels lateraux Download PDF

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Publication number
WO2007066353A2
WO2007066353A2 PCT/IN2006/000218 IN2006000218W WO2007066353A2 WO 2007066353 A2 WO2007066353 A2 WO 2007066353A2 IN 2006000218 W IN2006000218 W IN 2006000218W WO 2007066353 A2 WO2007066353 A2 WO 2007066353A2
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WIPO (PCT)
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radical
optionally substituted
valent
molecular formula
polymers
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PCT/IN2006/000218
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English (en)
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WO2007066353A3 (fr
Inventor
Anil Kumar
Sarada Prasad Mishra
Rabindra Sahoo
P. G. Sreelekha
Jasmine
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Indian Institute Of Technology Bombay
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Publication of WO2007066353A2 publication Critical patent/WO2007066353A2/fr
Publication of WO2007066353A3 publication Critical patent/WO2007066353A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the invention relates to processable poly (3,4-propylenedioxythiophene)s having pendant functional groups, to their syntheses and to their processable oligo-, polyermic and copolymeric derivatives.
  • Intrinsically electronic conducting polymers owing to the considerable derealization of the D- electrons along the main chain exhibit non-linear optical properties and after oxidation or reduction are also good electrical conductors. These compounds have promising applications in data storage, optical signal processing, suppression of electromagnetic interference (EMI) and solar energy conversion, rechargeable batteries, light-emitting diodes, electrochromic windows and display panels, field-effect transistors, printed circuit boards, chemical and bio sensors and antistatic materials.
  • EMI electromagnetic interference
  • solar energy conversion rechargeable batteries
  • light-emitting diodes light-emitting diodes
  • electrochromic windows and display panels electrochromic windows and display panels
  • field-effect transistors printed circuit boards
  • chemical and bio sensors and antistatic materials chemical and bio sensors and antistatic materials.
  • poly(3,4-ethylenedioxythiophene) exhibit many interesting properties that include stability in oxidized and reduced states, low bandgap, high electrochromic contrast and rapid switching.
  • PEDT poly(3,4-ethylenedioxythiophene)
  • An overview of numerous poly(alkylenedioxythiophene) derivatives, in particular poly-3,4-(ethylene- 1 ,2-dioxy)thiophene derivatives, their monomers, syntheses and applications are discussed in detail in Adv. Mater. 12, 2000, 481-494.
  • U.S. Pat. No. 5,111,327 described substituted 3,4- alkylenedioxythiophenes and their conductive polymerization products.
  • a water dispersion of PEDT doped with poly(styrenesulfonate) (PSS) is available from H. C. Starck (A Bayer subsidiary) under the trade name of Baytron® P and from Elecon Inc. USA under the trade name ELEFLEXTM.
  • TDA used the block copolymer approach to make soluble PEDT derivative and are available under the trade name of AedotronTM and oligotronTM (US 0088032).
  • the composition or the solvent of the dispersions were modified in order to fine tune the properties (US 6,852,830; PCT WO 03/048227; PCT WO 03/048228).
  • the present invention is related to the processable poly(3,4-propylenedioxythiophene) derivatives wherein the solubility can be fine tuned from aqueous to organic solvents.
  • the key feature of the present invention is the ability to fine tune the structure of the monomer of molecular formula I (our co-pending patent application number 302/MUM/2005) which in turn fine tunes the properties of the polymers and copolymers.
  • the present invention provides processable poly(3,4-propylenedioxythiophene)s of the formula Il and III having pendant functional groups and its copolymers: to their syntheses and to their oligo-, polymeric and copolymeric derivatives.
  • Y -CH 2 OX, -L and - CH 2 OH.
  • R is a n-valent linear or branched, optionally substituted, aliphatic C1-
  • Cn radical an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • X is a n-valent linear or branched, optionally substituted, aliphatic CI-Cn radical, an n- valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical (except benzylic or benzylic derivatives when R is a methyl group); -
  • R 1 is a n-valent linear or branched, optionally substituted, aliphatic CI-Cn radical, an n- valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R" is hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R'" is hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R" is hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic CI-Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R is L or hydrogen or is a n-vending linear or branched, optionally substituted, aliphatic C1- Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R is a n-vending linear or branched, optionally substituted, aliphatic C2-Cn radical, an n- valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • the invention provides processable (oxidized and reduced forms) poly(3,4- propylenedioxythiophene)s of the formula Il and III having pendant functional groups and its copolymers of formula II, III and IV.
  • Y, R and F are as defined above.
  • A is hydrogen or is an n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • B is hydrogen or is an n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • C is hydrogen or is an n-valent linear or branched, optionally substituted, aliphatic CI -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • D is hydrogen or is an n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • the present invention provides a practical solution to the ability to fine tune the processability of the poly(3,4-propylenedioxythiophene)s derivatives and its copolymers.
  • the invention further provides processable derivatives of poly(3,4- propylenedioxythiophene)s.
  • STEP B reacting the polymers obtained in step A with reducing agents in various solvents to produce reduced polymers of molecular formula III.
  • the syntheses of reduced polymer of molecular formula III is achieved in STEP C in which halogenation of monomers of molecular formula I using various reagents in organic solvents is carried out to produce 2,5-dihalogenated compounds of molecular formula X which in STEP D is polymerized in reductive polymerization conditions using various reagents in organic solvents to produce reduced polymer of molecular formula III.
  • the synthesis of polymers of molecular formula V is achieved in STEP E by the oxidative polymerization of the monomers of molecular formula 1 with varying amounts of EDT compounds of molecular formula Xl under various conditions with different oxidizing agents in presence of solvent to produce oxidized polymers of molecular formula IV which in STEP F is reduced with various reducing agents in various solvents to produce reduced polymers of molecular formula V.
  • STEP H Oxidative polymerization of the monomers of molecular formula 1 with varying amounts of monomer of molecular formula XIII under various conditions with different oxidizing agents in presence of solvent to produce oxidized polymers of molecular formula Vl;
  • STEP I reacting the polymers obtained in step H with reducing agents in various solvents to produce reduced polymers of molecular formula VII.
  • STEP K Oxidative polymerization of the monomers of molecular formula 1 with varying amounts of monomer of molecular formula Xl and XIII under various conditions with different oxidizing agents in presence of solvent to produce oxidized polymers of molecular formula VIII;
  • STEP L reacting the polymers obtained in step A with reducing agents in various solvents to produce reduced polymers of molecular formula IX.
  • the syntheses of reduced polymer of molecular formula IX is achieved in STEP M by reductive polymerization of monomers of molecular formula X with varying amounts of monomers of molecular formula XII and XIV using various reagents in organic solvents to produce polymers of molecular formula IX.
  • the oxidative polymerization in steps A, E, H and K can be achieved either by oxidative chemical or by oxidative electrochemical polymerization route.
  • Oxidative Chemical Polymeriztation The oxidative chemical polymerization is similar to that of other thiophenes or 3,4-alkylenedioxythiophene derivatives and is known to those skilled in the art and described in detail in the literature (Adv. Mater. 12 (7), 2000, 481-494).
  • Suitable chemical oxidizing agents are those known from the prior art for polythiophene preparation, for example iron(lll) compounds such as FeCI 3 or iron(lll) salts of organic acids like Fe(OTs) 3 , or potassium permanganate, manganese dioxide (MnO 2 ), potassium (di)chromate or peroxodisulphates (persulphates), such as Na 2 S 2 O 8 or K 2 S 2 O 8 , or (NI-U) 2 S 2 O 8 and also H 2 O 2 .
  • the oxidative polymerization can be carried out either under dry atmosphere conditions or under open-air conditions.
  • the oxidative polymerization of thiophene requires 2.25 equivalents of oxidation agent per mole of thiophene of formula 1 (J. Poly. Sci. Poly. Chem. Ed. 26, 1988, 1287-1294). In practice, 0.1 to 2 equivalent of oxidizing agent can be used per polymerizable unit. Furthermore, the oxidative chemical polymerization route proceeds slowly, which allows the application of the paste/solution, resulted from the mixing of the monomers and oxidant, to the substrate to be coated. After application of such paste/solutions, the oxidative chemical polymerization route can be accelerated by heating the coated substrate as disclosed in US 6,001 , 281 and WO 00/14139.
  • reaction procedures are those in which the thiophene monomer is initially introduced and the oxidizing agent is metered in in portions or continuously so that more than 1.998 mol, at the most, of the oxidizing agent cannot be present at any time per mole of monomer in addition to the monomer.
  • the reaction is carried out in such a way that the molar ratio of oxidizing agent to monomer is substantially less than 1.998:1 during the entire reaction time.
  • the process according to the invention can be carried out at room temperature. However, it may also be expedient to work at lower temperatures, e.g. 0 0 C, or at higher temperatures, e.g. at the reflux temperature of chloroform (about 60 0 C.) or an even higher temperature, which is possible, for example, in chlorobenzene. Typically, 0 to 100 0 C is employed, preferably 0 to 65 0 C.
  • the yield of desired neutral polythiophene can be increased if a base is added in at least equimolar amounts during the reaction for neutralizing acids (p-toluenesulphonic acid or HCI) formed from the oxidizing agent.
  • Suitable bases are, for example, ammonia, amines or basic metal oxides.
  • alkali metal or alkaline earth metal carbonates e.g. sodium carbonate, potassium carbonate or calcium carbonate, are preferably used. In their preparation, after a chemical polymerization, it may be necessary to wash out the salts, i.e.
  • an organic solvent is preferably used, in particular a halogenated hydrocarbon is used.
  • a halogenated hydrocarbon from the group consisting of chloroform, methylene chloride, tetrachloroethane, fluorohydrocarbons and chlorobenzene is very particularly preferably used.
  • organic solvents used can be ketones such as acetophenone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, nitriles such as acetonitrile and benzonitrile, sulfoxides such as dimethylsulfoxide, sulfones such as dimethylsulfone, phenylmethylsulfone and sulfolan, liquid aliphatic amides such as methyl acetamide, dimethyl ac ⁇ tamide, dimethyl formamide, pyrrolidone, N-methyl-pyrrolidone, caprolactam, N-methyl- caprolactam, aliphatic and mixed aliphatic and aromatic ethers such as diethylether and anisole, liquid ureas such as
  • Oxidative polymerization can also be carried out in aqueous or organic micellar or emulsion systems in order to get directly the conducting paints.
  • Oxidative Electrochemical Polymerization Electrochemical oxidative polymerization can be carried out at temperatures from -78 0 C. to the boiling point of the solvent employed, temperatures between -20 0 C. and 60 0 C is preferred.
  • reaction time depending upon the particular 3,4-propylenedioxythiophene, is generally between a few seconds and several hours. Electrochemical polymerization of 3,4-propylenedioxythiophene compounds was described in 1994 by Dietrich et al. (Journal Electroanalytical Chemistry, 1994, 369, 87-92).
  • Inert liquids suitable for use during electrochemical oxidation of 3,4-propylenedioxythiophene compounds according to formula (I) are: water, alcohols such as methanol and ethanol, ketones such as acetophenone, halogenated hydrocarbons such as methylene chloride, chloroform, tetrachloromethane and fluorohydrocarbons, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, nitriles such as acetonitrile and benzonitrile, sulfoxides such as dimethylsulfoxide, sulfones such as dimethylsulfone, phenylmethylsulfone and sulfolan, liquid aliphatic amides such as methyl acet
  • Electrolyte additives for use in the electrochemical polymerization are preferably free acids or the usual conducting salts, which exhibit a certain solubility in the solvent used.
  • Particularly suitable electrolytes are alkali, alkaline earth or optionally alkylated ammonium, phosphonium, sulfonium or oxonium cations in combination with perchlorate, tosylate, tetrafluoroborate or hexafluorophosphonate anions.
  • the electrolyte additives are used in such quantities, that a current of at least 0.1 mA flows during electrochemical oxidation. Electrochemical polymerization can be carried out continuously or discontinuously.
  • Electrode materials are ITO-covered glass, precious metal or steel mesh, carbon-filled polymers, evaporated metal-coated insulator layers and carbon felt. Current densities during electrochemical oxidation may vary within wide limits (0.0001 to 100 mA/cm 2 ).
  • L can be carried out using various reducing agents selected from the list: ammonia, hydrazine hydrate, and other organic reducing agents etc.
  • the organic phase after the reduction is then removed and extracted with 0.05 molar aqueous EDTA solution before isolating the polymer either by filteration or by precipitation in a non-solvent.
  • Halogenation in step C can be carried out using NCS, NBS, Br 2 and I 2 in various organic solvents like DMF, THF, hydrocarbons and halogenated hydrocarbons.
  • Reductive polymerization in steps D, G, J and M can be carried out using stille (organotin) routes or Suzuki routes as disclosed previously (Tetrahedron Letters, 2001 , 42, 155-157; Macromolecules, 1998, 31 , 2047-2056) or with nickel complexes as disclosed earlier (Bull. Chem. Soc. Japan, 1999, 72, 621 ; Advanced Materials, 1998, 10, 93-116).
  • the reduced polymers and copolymers (obtained through step D, G, J and M) can be redoped or oxidized using iodine or nitrosyl salts or antimony pentafluoride or any other oxidizing agent.
  • the two or the three or more different thiophene monomers may be arranged in blocks, alternatively or in an uncontrolled, random sequence, but preferably in an uncontrolled, random sequence in the oligomers and polymers.
  • Oligo- and poly(3,4-propylenedioxythiophene)s include all compounds in which more than one unit of the compounds according to the formulas above are linked to one another by polymerization or polycondensation, i.e. have a degree of polymerization 2 or above.
  • the transition from oligo- to the poly(3,4-propylenedioxythiophene)s with regard to the degree of polymerization is fluid.
  • the functional groups chosen in this disclosure are pendant allyl and propargyl groups.
  • the distribution and the concentration of the pendant functional group on the polymer backbone is controlled by the choice of appropriate starting monomer composition for polymerization.
  • These pendant functional groups can either be modified before the polymerization or after the polymerization with various monomeric and polymeric units generating a library of functional polymers.
  • the solubility of the functional polymers can also be fine tuned to be organic or aqueous soluble by appropriate choice of comonomers.
  • the polymer was found to be soluble in water and mixture of water and DMF.
  • the chemical nature of the polymer was confirmed using NMR spectroscopy. Electrochemical characterization revealed that the polymer is electroactive. Spectroelectrochemical studies gave a value of 70% for electrochromic contrast at maximum absorption with switching time of 1 second. The reduced polymer exhibited dark blue color whereas the oxidized polymer was found to be colored. The four probe conductivity measurements on the solution cast film gave a conductance value of 5 x 10 "6 S/cm which increases to 1 x 10 '2 S/cm on exposure to iodine.
  • This polymer was blend with various water soluble polymers in various compositions to get solutions of very high to low viscosity. Free standing films of these blends were found to be semiconducting in nature.
  • the polymerization was initiated by the addition of 2 mg of 3,4-ethylenedioxythiophenetthe followed by slow addition of a solution of TBAP (5 eq) in water (3 mL) during 2h.
  • the reaction mixture was allowed to stir at room termperature for 4 days followed by dialysis to remove the oligomers and initiator.
  • the solution so obtained was stirred with ammonia solution in order to dedope the polymer formed.
  • the final reduced form of the polymer was obtained by evaporation of water under reduced pressure.
  • the chemical nature of the polymer was confirmed using NMR spectroscopy. Electrochemical characterization revealed that the polymer is electroactive.
  • Electrochemica polymerization of diallyl ProDOT was done in acetonitrile taking 0.02 M solution of monomer and TBAP as supporting electrolyte by scanning the potential between -0.6 and 1.3 V. Monomer oxidation was occurred at 1.2 V vs Ag/Ag + . CV of the polymer was recorded between -0.6 to 0.8 V. The linear relationship between the peak current and the scanning rate indicated the formation of a redox active and well adhered polymer on the electrode.
  • the spectroelectrochemical studies of the polymer were carried out using ITO coated glass as a working electrode. The polymer was formed by applying a static potential of 1.3 V. Two peaks were observed at 580 and 637 nm at -1 V and the color was observed blue. At +1 V, these two peaks disappear and color changes to transparent. Contrast of the polymer between completely reduced state and completely oxidized state was calculated 76%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

La présente invention concerne des poly(3,4-propylènedioxythiophènes) pouvant être transformés répondant aux formules II et III ayant des groupes fonctionnels latéraux; leurs synthèses et leurs dérivés oligomères, polymères et copolymères. Formules (II) et (III). La présente invention concerne en outre les procédés de préparation desdits composés.
PCT/IN2006/000218 2005-06-28 2006-06-19 Nouveaux polymeres de derives 3,4-propylenedioxythiophene ayant des groupes fonctionnels lateraux WO2007066353A2 (fr)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009094361A2 (fr) * 2008-01-21 2009-07-30 University Of Connecticut Polymères conjugués de 3,4-propylènedioxythiophène substitué, leur composition, leur procédé de fabrication et leur utilisation
WO2011081340A1 (fr) * 2009-12-30 2011-07-07 Korea University Research And Business Foundation Polymères électriquement conducteurs solubles dans l'eau
WO2012027348A2 (fr) 2010-08-27 2012-03-01 University Of Delaware Monomères substitués de 3,4-propylènedioxythiophène, agents de réticulation à base de 3,4-propylènedioxythiophène et polymères en contenant
JP2012077218A (ja) * 2010-10-04 2012-04-19 Japan Carlit Co Ltd:The 重合性モノマー組成物、固体電解コンデンサの製造方法
US8513377B2 (en) 2011-03-02 2013-08-20 The University Of Connecticut Selenium-based monomers and conjugated polymers, methods of making, and use thereof
WO2014188090A1 (fr) * 2013-05-23 2014-11-27 Centre National De La Recherche Scientifique Materiau superoleophobe et/ou superhydrophobe, son procede de preparation et ses applications
WO2017011822A1 (fr) * 2015-07-16 2017-01-19 Georgia Tech Research Corporation Polymères aptes a la mise en œuvre, leurs procédés de production et utilisation
US9680102B2 (en) 2010-03-25 2017-06-13 University Of Connecticut Formation of conjugated polymers for solid-state devices
US9944757B2 (en) 2012-07-23 2018-04-17 The University Of Connecticut Electrochromic copolymers from precursors, method of making, and use thereof
US10323178B2 (en) 2014-05-16 2019-06-18 The University Of Connecticut Color tuning of electrochromic devices using an organic dye
CN112876655A (zh) * 2020-01-17 2021-06-01 长兴材料工业股份有限公司 导电性高分子材料及其用途
CN113423755A (zh) * 2019-02-07 2021-09-21 马丁·舍丁 导电氧化还原低聚物
EP4151640A1 (fr) * 2021-09-20 2023-03-22 Heraeus Deutschland GmbH & Co. KG Procédé de production de polythiophènes fonctionnalisés

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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009094361A3 (fr) * 2008-01-21 2009-10-29 University Of Connecticut Polymères conjugués de 3,4-propylènedioxythiophène substitué, leur composition, leur procédé de fabrication et leur utilisation
US7951902B2 (en) 2008-01-21 2011-05-31 The University Of Connecticut Conjugated polymers from substituted 3,4-propylenedioxythiophene, compositions, method of making, and use thereof
WO2009094361A2 (fr) * 2008-01-21 2009-07-30 University Of Connecticut Polymères conjugués de 3,4-propylènedioxythiophène substitué, leur composition, leur procédé de fabrication et leur utilisation
US8535571B2 (en) 2009-12-30 2013-09-17 Korea University Research And Business Foundation Water-soluble electrically conductive polymers
WO2011081340A1 (fr) * 2009-12-30 2011-07-07 Korea University Research And Business Foundation Polymères électriquement conducteurs solubles dans l'eau
US9243111B2 (en) 2009-12-30 2016-01-26 Korea University Research And Business Foundation Water-soluble electrically conductive polymers
US9680102B2 (en) 2010-03-25 2017-06-13 University Of Connecticut Formation of conjugated polymers for solid-state devices
EP2616472A2 (fr) * 2010-08-27 2013-07-24 University Of Delaware Monomères substitués de 3,4-propylènedioxythiophène, agents de réticulation à base de 3,4-propylènedioxythiophène et polymères en contenant
EP2616472A4 (fr) * 2010-08-27 2014-02-19 Univ Delaware Monomères substitués de 3,4-propylènedioxythiophène, agents de réticulation à base de 3,4-propylènedioxythiophène et polymères en contenant
WO2012027348A2 (fr) 2010-08-27 2012-03-01 University Of Delaware Monomères substitués de 3,4-propylènedioxythiophène, agents de réticulation à base de 3,4-propylènedioxythiophène et polymères en contenant
JP2012077218A (ja) * 2010-10-04 2012-04-19 Japan Carlit Co Ltd:The 重合性モノマー組成物、固体電解コンデンサの製造方法
US8513377B2 (en) 2011-03-02 2013-08-20 The University Of Connecticut Selenium-based monomers and conjugated polymers, methods of making, and use thereof
US8822635B2 (en) 2011-03-02 2014-09-02 The University Of Connecticut Selenium-based monomers and conjugated polymers, methods of making, and use thereof
US9944757B2 (en) 2012-07-23 2018-04-17 The University Of Connecticut Electrochromic copolymers from precursors, method of making, and use thereof
FR3005956A1 (fr) * 2013-05-23 2014-11-28 Centre Nat Rech Scient Materiau superoleophobe et/ou superhydrophobe, son procede de preparation et ses applications
WO2014188090A1 (fr) * 2013-05-23 2014-11-27 Centre National De La Recherche Scientifique Materiau superoleophobe et/ou superhydrophobe, son procede de preparation et ses applications
US10323178B2 (en) 2014-05-16 2019-06-18 The University Of Connecticut Color tuning of electrochromic devices using an organic dye
WO2017011822A1 (fr) * 2015-07-16 2017-01-19 Georgia Tech Research Corporation Polymères aptes a la mise en œuvre, leurs procédés de production et utilisation
JP2018530908A (ja) * 2015-07-16 2018-10-18 ジョージア テック リサーチ コーポレイションＧｅｏｒｇｉａ Ｔｅｃｈ Ｒｅｓｅａｒｃｈ Ｃｏｒｐｏｒａｔｉｏｎ 処理可能なポリマー、及びその製造方法と使用方法
US10882949B2 (en) 2015-07-16 2021-01-05 Georgia Tech Research Corporation Processable polymers and methods of making and using thereof
CN113423755A (zh) * 2019-02-07 2021-09-21 马丁·舍丁 导电氧化还原低聚物
EP3921359A4 (fr) * 2019-02-07 2022-05-25 Martin Sjödin Oligomères redox conducteurs
CN112876655A (zh) * 2020-01-17 2021-06-01 长兴材料工业股份有限公司 导电性高分子材料及其用途
US20210221933A1 (en) * 2020-01-17 2021-07-22 Eternal Materials Co., Ltd. Conductive polymer material and use thereof
CN112876655B (zh) * 2020-01-17 2023-09-29 长兴材料工业股份有限公司 导电性高分子材料及其用途
EP4151640A1 (fr) * 2021-09-20 2023-03-22 Heraeus Deutschland GmbH & Co. KG Procédé de production de polythiophènes fonctionnalisés
WO2023041228A1 (fr) * 2021-09-20 2023-03-23 Heraeus Deutschland GmbH & Co. KG Procédé de production de polythiophènes fonctionnalisés

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