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WO2001018090A1 - Polymeres contenant des groupes heterocycliques, procede de fabrication, leur utilisation en couche et composes heterocycliques - Google Patents

Polymeres contenant des groupes heterocycliques, procede de fabrication, leur utilisation en couche et composes heterocycliques

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Publication number
WO2001018090A1
WO2001018090A1 PCT/EP2000/007971 EP0007971W WO0118090A1 WO 2001018090 A1 WO2001018090 A1 WO 2001018090A1 EP 0007971 W EP0007971 W EP 0007971W WO 0118090 A1 WO0118090 A1 WO 0118090A1
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WO
WIPO (PCT)
Prior art keywords
aryl
alkyl
group
formula
atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/007971
Other languages
English (en)
Inventor
Hermannus F. M. Schoo
Dagobert M. De Leeuw
Peter T. Herwig
Wolter Ten Hoeve
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke Philips NV
Original Assignee
Koninklijke Philips Electronics NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Koninklijke Philips Electronics NV filed Critical Koninklijke Philips Electronics NV
Publication of WO2001018090A1 publication Critical patent/WO2001018090A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring

Definitions

  • the invention relates to a method of preparing a polymer containing heterocyclic groups, which polymer predominantly comprises structural units of formula (I),
  • - X is selected from the group formed by an oxygen atom and a sulphur atom and a N(R 2 ) group, wherein R 2 is selected from the group formed by a hydrogen atom and an alkyl group, aryl group, alkyl-aryl group and aryl-alkyl group, and
  • R 3 and R 4 may be equal and are selected from the group formed by a hydrogen atom, chlorine atom, bromium atom, fluorine atom and iodide atom, and from a C 1 -C 4 alkyl group, a carbonitrile group, trihalomethyl group, hydroxy group, nitro group, amino group, carboxyl group, sulphoxyl group, sulphonate group and carbonate group and from a substituted and an unsubstituted phenyl group, alkyl-aryl group and aryl-alkyl group, alkoxy group and thioalkoxy group.
  • the invention further relates to heterocyclic compounds and polymers with heterocyclic groups in the chain.
  • the invention also relates to a method of manufacturing a layer from such a polymer.
  • the invention finally relates to a transistor comprising a semiconductive layer of such a polymer.
  • Such a method of preparing a polymer of formula I of the formula sheet is known from EP-A-0182548.
  • An example of such a polymer is unsubstituted polythienylene- vinylene.
  • This is the polymer of formula I wherein R 3 and R are a hydrogen atom (H) and X is a sulphur atom (S), which will hereinafter also be referred to as PTV.
  • This polymer can be used as a semiconductive material in a transistor.
  • the starting substance is a compound of formula II,
  • R 3 and R 4 have the same meaning as in formula I;
  • Y and Y' are each selected from the group formed by a chlorine atom, a bromium atom, a fluorine atom and an iodide atom and from a p-toluene sulphoxyl group and a halogen- substituted methyl sulphoxyl group.
  • This starting substance reacts in known manner with an excess of thioether to form a sulfonium salt, for example 2,5-bis (methyl diethyl sulfonium bromide)thiophene.
  • This salt is used as a monomer in the polymerization step, which yields a precursor polymer with a sulfonium salt as the side group at the chain of the polymer.
  • a polymer of formula I is obtained.
  • a drawback of this method resides in that a transistor wherein the polymer formed, in particular PTV, is used as a semiconductor material has a poor "on-off ratio" of electric current. This ratio is an impediment to the use of the transistor as a switch. The ratio means that many of the current-carrying electrons in the polymer do not contribute to the transmission of current. This limited contribution can be attributed to the absence of an ordering or crystalline structure in the polymer and the large degree of branching of the molecules of the polymer formed in this method.
  • this object is achieved by the following steps: a reaction of the compound of formula II with a thiol RiSH to form an intermediate product of formula III,
  • - Ri is selected from the group formed by a substituted and an unsubstituted alkyl group, aryl group, alkyl-aryl group and aryl-alkyl group;
  • X, Y, R 3 and R 4 have the same meaning as in formula II; oxidation of at least a fraction of the intermediate product to a monomer or a mixture of monomers of formula IV,
  • Rj, R 3 , R 4 , X and Y have the same meaning as in formula III, and wherein m is equal to 1 or 2; polymerization of the monomer or of a mixture of monomers of formula IV or of a mixture of monomers of formula IV and the intermediate product of formula III to form a precursor homopolymer or copolymer comprising structural units of formula V,
  • - q is either 0, 1 or 2, but in at least a fraction of the units, q is 1 or 2;
  • the method comprises a reaction step, an oxidation step, a polymerization step and an elimination step.
  • the reaction step of the method the reaction of the starting substance with a thiol leads to the formation of a thioether as the intermediate product.
  • the intermediate product is partly or completely oxidized to a compound of formula IV, which comprises a sulphinyl group or a sulphonyl group, or to a mixture of these compounds.
  • a peracid such as m-chloroperbenzoic acid
  • hydrogen peroxide and tellurium oxide may be used as the oxidation agent.
  • a first advantage of this method resides in that the intermediate product of formula V is not charged.
  • this product is less sensitive to the occurrence of undesirable side reactions, as compared to the sulfonium ion in accordance with the state of the art.
  • the reaction step can be readily carried out.
  • substitution of a single group Y per molecule undesirable polymerization reactions between RiS groups are precluded. The result is an at least substantially linear polymer.
  • the polymerization step to form a polymer comprising structural units of formula V takes place by the addition of a base.
  • the base can be added to a composition, either a solution or a fine dispersion, of a formula IV -monomer obtained in the oxidation step.
  • the base can also be added to a mixture of the monomers.
  • the base can further be added to a mixture of at least one of the monomers and the intermediate product.
  • the base can additionally be added to a mixture of compounds of formula IV and possibly formula III, which compounds have been independently obtained.
  • a copolymer is formed comprising structural units of formula V, which units may differ from each other as regards the Ri, R 3 , R 4 , and X-group and the value of q.
  • the method in accordance with the invention is also based on the recognition that the hydrogen atoms at the carbon atom between the sulphur atom and the heterocyclic ring are acid. As a result, proton transfer from the monomer to the base is easy. It is assumed that the halogen atom splits off from this deprotonated monomer in the form of a halogenide ion, whereafter the actual polymerization takes place. Presumably, this polymerization takes place via a radical mechanism. To preclude that the base carries out a substitution at the location of the halogen atom, the choice of a non-nucleophilic base is desirable. An example of such a base is tert-butyloxide. Another example is a tertiary amine.
  • the precursor homopolymer or copolymer is converted, in the elimination step, into a polymer by means of heat, which polymer predominantly comprises structural units of formula I.
  • an aromatic and a Cj to C 10 aliphatic thiol are selected as the thiol RjSH.
  • the Ri group may be branched and substituted. Substituents are, inter alia, halogen, amino, nitro, hydroxy, alkoxy, carbonate and sulphonate groups.
  • the choice of the thiol RiSH appears to be non-critical relative to one or more steps in the method according to the invention. This is based on the assumption that substitutions in the Ri group on a ⁇ , ⁇ or further atom with respect to the sulphur atom, do not cause interaction between the sulphur atom and the substituent.
  • This variety of thiols RiSH enables a thiol to be chosen which has favorable side effects.
  • examples of such effects are the solubility of intermediate products and monomers in a solvent such as water or alcohol; the stability of the precursor monomer's group S(O) m R ⁇ to be eliminated, where m is equal to 1 or 2 and not necessarily the same for all groups within a precursor polymer; the volatility of the group S(O) m R ⁇ or reaction products thereof in a vacuum, in a nitrogen atmosphere and in air; and the use of the group S(O) m Rj as an additive in the polymer formed.
  • the example of the solubility in water seems to be practicable by choosing a Ri group which is substituted with one or more polar groups as hydroxy and amino groups.
  • the method in accordance with the invention leads to novel heterocyclic compounds of formula VI and precursor polymers with heterocyclic groups in the chain, which groups are structural units of formula V.
  • the method in accordance with the invention additionally leads to novel copolymers comprising, as structural units, the units of formulae I and VII.
  • Such a polymer apparently has the advantage that it is less sensitive to oxygen absorption. Supposedly, an absorbed oxygen molecule links to a conjugated chain, causing the conduction in the chain to be annihilated.
  • the copolymer has more, yet smaller, conjugated chain parts. As a result of the larger number of conjugated chain parts, the relative influence of the linkage of one oxygen molecule is smaller. This causes the stability of the conductance of the polymer to be increased.
  • a further object of the invention is to provide a method of manufacturing a layer of a polymer as described in the opening paragraph, which method can be readily carried out. This object of the invention is achieved in a method comprising:
  • Ri is selected from the group formed by a substituted and an unsubstituted alkyl, aryl, alkyl aryl and aryl alkyl group; q is selected from the group formed by 0, 1 and 2 but is equal, in at least one fraction of the units, to 1 or 2;
  • R 3 and R 4 have the same meaning as in formula I; the conversion of the precursor polymer applied in the form of a layer to a polymer which predominantly comprises structural units of formula I by applying heat.
  • This method in accordance with the invention can be readily carried out because the precursor polymers with structural units of formula V can be readily dissolved in solvents such as tetrahydrofuran and chlorinated hydrocarbons. As a result of said solubility, the necessary amount of solvents can be reduced and a filtration step omitted. In addition, HCl gas does not have to be used in the elimination step. In the method known from an article by H. Murata et. al., Synthetic metals 36 (1990), 95-102, wherein a precursor polymer with alkoxy and hydroxy side groups is employed, HCl gas must be used.
  • Layers manufactured by means of the method in accordance with the invention have the additional advantage that they possess excellent electrical properties.
  • a transistor in which the PTV layer formed by means of the method is used as a semiconductor has a high on-off ratio of electric current.
  • the mobility of electric charge under the influence of an electric field i.e. the mobility
  • this precursor polymer, and probably also the PTV are largely unbranched. This can be attributed to the satisfactory solubility of the precursor polymer.
  • similar polymers in accordance with the invention comprising pyrrole groups or furan groups possess similar properties. The reason for this being that these polymers too are largely unbranched and, according to Brown et. al., Synthetic metals 88 (1997), 48, the mechanism of movement of electric charge is independent of the heterocyclic atom in the chain of the polymer.
  • a substrate obtained using the method in accordance with the invention which comprises a layer of a polymer with structural units of formula I, can be used as a semiconductor in a transistor.
  • a transistor comprising such a semiconductor has a high "on- off ratio.
  • the use of a layer of such a polymer, in particular PTV, is favorable as compared to other semiconductors owing to the "stack integrity". This means that the layer can be used as a substrate for a subsequent layer.
  • Such a transistor may form part of an integrated circuit and can be used therein, inter alia, as a switch or a memory unit.
  • Fig. 1 is a diagrammatic, cross-sectional view of a transistor
  • Fig. 2 is a diagram of the current through a transistor comprising a semiconductive PTV layer prepared by means of the method in accordance with the invention, as a function of the voltage applied at the gate electrode;
  • Fig. 3 is a diagram of the mobility in a transistor comprising a semiconductive PTV layer prepared in accordance with the method of the invention, as a function of the voltage applied at the gate electrode.
  • Fig. 4 shows a reaction scheme of the polymerization step of a method in accordance with the invention.
  • Example 1 synthesis of 2-butylsulphinylmethyl-5-chloromethylthiophene
  • sodium hydroxide tablets (14.0 g, 0.35 mol) are added to an ice-cooled mixture of 2,5-(bischloromethyl)thiophene (68.6 g, 0.379 mol, distilled material from the chloromethylation of thiophene, not entirely pure) and n-butanethiol (36 ml, 0.336 mol) in 175 ml.
  • the mixture is stirred overnight, whereby the temperature rises to room temperature. Subsequently, the mixture is heated to 50-60 °C for a number of hours, while stirring sufficiently. The remaining thiol is evaporated. The residue is treated with hexane/toluene and water, leading to the formation of two layers. The layers are separated.
  • m-chloroperbenzoic acid (m-CPBA, 40 g 70%, 0.16 mol) is added in small quantities to a cold solution of the product of formula VIII (37.6 g 0.16 mol) in 200 ml dichloromethane.
  • the reaction is exothermal and a white suspension is formed.
  • the reaction mixture is added to diluted sodium hydroxide solution. Layers are formed, which are subsequently separated from each other. The organic layer is washed with water and dried. The organic solvent is evaporated. The residue is purified by column chromatography wherein use is made of silica and, as an eluent, a mixture of hexane and ethylacetate.
  • sodium hydroxide tablets (14.0 g, 0.35 mol) are added to an ice-cooled mixture of 2,5-bis(chloromethyl)thiophene and 34 ml thiophenol (0.33 mol) in 175 ml.
  • the ice bath is removed and the mixture is stirred for 12 hours, whereafter it is heated to 50-60 °C for 24 hours.
  • liquid is evaporated.
  • the residue is dissolved in a mixture of hexane and toluene. After washing three times with water, a drying operation is carried out. The residue is stirred with a solution of toluene in hexane, leading to precipitation.
  • the solid is filtered and washed with hexane.
  • the hexane in the filtrate is evaporated while stirring.
  • the filtrate is subsequently heated to 0.1 mbar to remove the 2,5- bischloromethylthiophene.
  • the product is characterized by proton-NMR, which shows that the ratio between the groups CH 2 C 6 H 5 :CH 2 C1 ranges from approximately 1.5 to 1. This means that approximately 0.187 mol of 2-phenylthiomethyl-5-chloromethylthiophene is formed and approximately 0.047 mol of a side product, namely 2,5- bis(phenylthiomethyl)thiophene .
  • this mixture is used in the oxidation step.
  • the mixture is dissolved in 400 ml dichloromethane and subsequently cooled to a temperature below 10 °C.
  • a quantity of 70 g of 70% m-CPBA (0.28 mol) is added in small quantities.
  • the mixture is stirred for one hour, whereby the temperature rises to 7 °C.
  • 250 ml of diluted sodium hydroxide solution is added.
  • the layers formed are separated.
  • the organic layer is washed twice with water.
  • the layer is subsequently dried.
  • the organic solvent is evaporated.
  • the residue is purified, using silica and, as an eluent, a mixture of ethylacetate and hexane.
  • Example 3 synthesis of a precursor polymer A degassed solution of 1 g (3.7 mmol) 2-phenylsulphinylmethyl-5- chloromethylthiophene, i.e. a compound of formula XI, in 15 ml of a 1 :5 mixture of dry sec- BuOH and THF is cooled to a temperature below M0 °C in a nitrogen atmosphere.
  • Example 4 preparation of a layer of PTV, and properties of said layer
  • the source-drain current through the PTV layer is measured as a function of the "gate" voltage V g in the linear regime and in the saturation regime, whereby "drain” voltages V d of, respectively, -2 and -20 V are used.
  • the on-off ratio is found to be 10 6 , which is a high value.
  • Example 5 the structure of a transistor with PTV
  • the transistor 1 shown in Fig. 1 comprises an electrically insulating substrate 2, which supports a first layer 3 of a polymer material, for example polyaniline, which comprises electroconductive parts and accommodates a source electrode 31 and a drain electrode 32.
  • the electrically non-conducting parts of the first layer 3 can be removed.
  • the organic semi-conductive layer 4 comprising polythienylene-vinylene prepared by means of the method in accordance with the invention, has a channel 41, the length of the channel being indicated by number 411.
  • An electrically insulating layer 5, for example of polyvinylphenol, covers the layer 4 and insulates the gate electrode 61 with respect to the channel 41.
  • the gate electrode forms part of a second conductive layer 6 which is made, for example, of doped polyaniline. The electrically non-conducting parts of this second conductive layer can be removed.
  • field effect transistors include "bottom-gate” structures and transistors with other organic polymers or non-polymeric layers for the insulating and conducting parts.
  • the transistor may form part of a larger circuit, such as an inverter, an oscillator or an integrated circuit.
  • a field effect transistor a bipolar transistor with a semiconductive layer of polythienylene-vinylene has been prepared in accordance with the method of the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé facile pour préparer un polythiénylène-vinylène et des composés apparentés contenant des groupes hétérocycliques dans la chaîne polymère, lesdits composés possédant des propriétés structurelles et électriques améliorées. Le procédé consiste à faire réagir un composé hétérocyclique 2,5-bishalométhyl-substitué avec un thiol, à effectuer une oxydation et une polymérisation pour arriver à un nouveau polymère précurseur comprenant des unités structurelles correspondant à la formule (V). L'élimination thermique permet d'obtenir un polythiénylène-vinylène, qui peut être appliqué sous la forme d'une couche à un substrat et utilisé comme un matériau semi-conducteur dans un transistor.
PCT/EP2000/007971 1999-09-02 2000-08-15 Polymeres contenant des groupes heterocycliques, procede de fabrication, leur utilisation en couche et composes heterocycliques Ceased WO2001018090A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99202851.4 1999-09-02
EP99202851 1999-09-02

Publications (1)

Publication Number Publication Date
WO2001018090A1 true WO2001018090A1 (fr) 2001-03-15

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092369A1 (fr) * 2000-05-30 2001-12-06 Koninklijke Philips Electronics N.V. Procede pour preparer un polymere, procede pour preparer un compose, composes, polymeres et procede pour fabriquer un dispositif electronique
US6392785B1 (en) 1997-08-28 2002-05-21 E Ink Corporation Non-spherical cavity electrophoretic displays and materials for making the same
WO2002096970A1 (fr) * 2001-05-29 2002-12-05 Koninklijke Philips Electronics N.V. Polymere, methode de preparation, et dispositif electronique
US6738050B2 (en) 1998-05-12 2004-05-18 E Ink Corporation Microencapsulated electrophoretic electrostatically addressed media for drawing device applications
US6839158B2 (en) 1997-08-28 2005-01-04 E Ink Corporation Encapsulated electrophoretic displays having a monolayer of capsules and materials and methods for making the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900782A (en) * 1988-04-04 1990-02-13 Allied-Signal Inc. Stabilized polyelectrolyte precursors of poly(aromatic and heteroaromatic vinylenes)
US5053166A (en) * 1986-02-18 1991-10-01 Agency Of Industrial Science & Technology Hetero-arylene vinylene polymer and highly conductive composition thereof
EP0867437A1 (fr) * 1997-03-14 1998-09-30 Koninklijke Philips Electronics N.V. Procédé de préparation de composés conjugués contenant le thiophène ou le furanne et composés précurseurs utilisés dans celui-ci
US5917003A (en) * 1993-09-14 1999-06-29 Hoechst Aktiengesellschaft Process for producing polymers of α,ω-unsaturated conjugated compounds, and high molecular weight conjugated polymers thus obtainable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5053166A (en) * 1986-02-18 1991-10-01 Agency Of Industrial Science & Technology Hetero-arylene vinylene polymer and highly conductive composition thereof
US4900782A (en) * 1988-04-04 1990-02-13 Allied-Signal Inc. Stabilized polyelectrolyte precursors of poly(aromatic and heteroaromatic vinylenes)
US5917003A (en) * 1993-09-14 1999-06-29 Hoechst Aktiengesellschaft Process for producing polymers of α,ω-unsaturated conjugated compounds, and high molecular weight conjugated polymers thus obtainable
EP0867437A1 (fr) * 1997-03-14 1998-09-30 Koninklijke Philips Electronics N.V. Procédé de préparation de composés conjugués contenant le thiophène ou le furanne et composés précurseurs utilisés dans celui-ci

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENG H, ELESENBAUMER R.L.: "New precursors and polymerization route for the preparation of high molecular mass poly(3,4-dialkoxy-2,5-thienylenevinylene)s: low band gap conductive polymers", J. CHEM. SOC.,CHEM. COMMUN., 1995, pages 1451 - 1452, XP002155489 *
PEETERS L ET AL: "Synthesis and Environmental Stability of Substituted Poly(thienylene vinylenes)", TRENDS IN POLYMER SCIENCE,NL,ELSEVIER SCIENCE PUBLISHERS B.V. AMSTERDAM, vol. 5, no. 5, 1 May 1997 (1997-05-01), pages 161 - 166, XP004064126, ISSN: 0966-4793 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6392785B1 (en) 1997-08-28 2002-05-21 E Ink Corporation Non-spherical cavity electrophoretic displays and materials for making the same
US6839158B2 (en) 1997-08-28 2005-01-04 E Ink Corporation Encapsulated electrophoretic displays having a monolayer of capsules and materials and methods for making the same
US6738050B2 (en) 1998-05-12 2004-05-18 E Ink Corporation Microencapsulated electrophoretic electrostatically addressed media for drawing device applications
WO2001092369A1 (fr) * 2000-05-30 2001-12-06 Koninklijke Philips Electronics N.V. Procede pour preparer un polymere, procede pour preparer un compose, composes, polymeres et procede pour fabriquer un dispositif electronique
JP2003535199A (ja) * 2000-05-30 2003-11-25 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ ポリマーの製造方法、化合物の製造方法、化合物、ポリマー、及び電子装置の製造方法
US7361716B2 (en) 2000-05-30 2008-04-22 Koninklijke Philips Electronics N.V. Method of preparing a polymer, method of preparing a compounds, compounds, polymers, and method of manufacturing an electronic device
WO2002096970A1 (fr) * 2001-05-29 2002-12-05 Koninklijke Philips Electronics N.V. Polymere, methode de preparation, et dispositif electronique

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