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GB2346148A - Conducting polymers with switchable magnetic/electronic properties - Google Patents

Conducting polymers with switchable magnetic/electronic properties Download PDF

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Publication number
GB2346148A
GB2346148A GB9901801A GB9901801A GB2346148A GB 2346148 A GB2346148 A GB 2346148A GB 9901801 A GB9901801 A GB 9901801A GB 9901801 A GB9901801 A GB 9901801A GB 2346148 A GB2346148 A GB 2346148A
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Prior art keywords
copolymers
polymer
dielectric anisotropy
pendant
electric field
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GB9901801A
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GB9901801D0 (en
GB2346148B (en
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John William Brown
Peter Jonathan Samuel Foot
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Publication of GB2346148A publication Critical patent/GB2346148A/en
Application granted granted Critical
Publication of GB2346148B publication Critical patent/GB2346148B/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular 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
    • C08G61/124Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • C08G73/026Wholly aromatic polyamines
    • C08G73/0266Polyanilines or derivatives thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124Intrinsically conductive polymers
    • H01B1/128Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0488Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a special bonding
    • C09K2019/0496Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a special bonding the special bonding being a specific pi-conjugated group
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam

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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)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

A range of copolymers is provided, which exhibit switching of their electrical and optical properties under the influence of external stimuli. The general structural feature of these materials is a conjugated f polymer backbone which may be semiconducting or conducting. The backbone is substituted with pendant mesogens and spacer groups in either sequential block or alternating copolymer arrangements. The switching properties of these systems arise from the tendency for mesogenic pendant groups with positive dielectric anisotropy to align parallel to the applied electric field and the pendant groups with negative dielectric anisotropy to align perpendicular to the applied field. These various alignments apply torque to the polymer backbone and interupt the conjugation of the polymer producing changes in electronic conduction and electrical properties.

Description

CONDUCTING POLYMERS WITH SWITHABLE MAGNETIC/ELECTRONIC PROPERTIES This invention relates to a range of copolymers which exhibit strong switching of their electrical and optical properties under the influence of external stimuli. The general structural feature of these materials is a conjugated X polymer backbone which may be semiconducting or conducting (i. e. one with an energy-gap between zero and about three electron volts in its unsubstituted form). The backbone is substituted with pendant mesogens and spacer groups of various lengths in either sequential block arrangements or altemating copolymer arrangements. (A typical example is shown in Figure 1.) The polymer backbone may advantageously comprise units of pyrrole, thiophene, aniline or carbazole. These may be substituted in some or all available positions with suitable flexible spacers, preferably an n-alkyl or n-alkyloxy chain of length between one and eighteen carbon atoms which may or may not be terminally substituted with a mesogenic moiety. Preferred repeat units are 3-or 3,4-substituted-2,5-pyrrole- or thiophenediyl, N-substituted 2,5-pyrrolediyl, 2-or 2,5-substituted anilinediyl or Nsubstituted 3,6-carbazolediyl. The mesogenic moieties are grouped in sequences of positive or negative dielectric anisotropies or may optionally have a dielectric anisotropy that is electric field frequency dependent.
The invention was based on research into : new, stable liquid crystal conducting polymers which have externally variable conduction arising from the application of an extemal electric or magnetic field when the polymer is in a liquid crystal phase. This results from the tendency for mesogenic side group molecules with positive dielectric anisotropy to align parallel to the applied electric field, and molecules with a negative dielectric anisotropy to align perpendicular to the applied field. Molecules with a frequency dependent dielectric anisotropy will have a molecular alignment which is dependent on the frequency of the electric field to which they are exposed. These various alignments will apply torque to the polymer backbone and interrupt the conjugation of the polymer producing changes in electronic conduction and electrical properties.
It has been found that these polymer systems have externally variable conduction when exposed to an extemal electric or magnetic field in their liquid crystal state. It has been found necessary in many cases to convert the polymer into the liquid crystal phase either by conventional bulk thermotropic methods or by the application of a focussed laser beam while simultaneously applying an electric or magnetic field. In the prior art [British Patent Applications GB 2304723 and GB 2318119] liquid crystal conducting polymers have been used to generate extemally variable conduction. Such systems should be distinguished from that in the present invention which in addition to developing self ordering properties arising from the liquid crystal phase allows the order and orientation in the liquid crystal and resulting polymer effective conjugation to be electrically or magnetically driven by extemal fieids. This results in much greater range of external variability in the conduction and switching properties of the polymer.
The potency of the electric or magnetic field variable alignment will depend on the symmetry and regularity of the aromatic or heteroaromatic repeating units in the polymer backbone. Thus, for a polymer in which the mesogenic group is attached to a repeating unit which is"reversible" (such as N-substituted poly (2,5-pyrrolediyl) or polycarbazole which have a plane of symmetry) the variability is readily obtainable. However, if for example the mesogenic group is attached to the 3-position of a thiophene monomer, the maximum beneficial effect of the present invention will only be obtained if the resulting polymer has been formed by a regiospecific polymerisation method. Such methods are well known in the prior art [e. g. TA Chen and RD Rieke, J.
Amer. Chem. Soc., 114, (1992), 10087.] and need not be detailed herein.
Synthesis Example 1 An example of a suitable synthetic route for the preparation of the pyrrole monomers is given in the following Schemes 1-5 which are subsequently polymerised, or oligomerised and subsequently polymerised in appropriate ratios.
All starting materials are known or prepared in analogy to known starting materials.
Other routes for the preparation of the potypyrrpies and other polymers and monomers are apparent to the skilled worker. All these steps and the corresponding reaction conditions are known to the skilled worker.
Fields of Application These materials would have potential applications in the production of polymer films of controllable conductivity, or as antistatic coatings, or as circuit boards on which the conducting tracks have been produced by a combination of laser and applied electric fields, or in a new generation of non-silicon base molecular microprocessors.

Claims (7)

  1. CLAIMS 1. Organic copolymers having a conjugated 7 : backbone, substituted with pendant mesogens and flexible spacer groups of various lengths in either sequential block or alternating copolymer arrangements, in which the mesogenic moieties are grouped in sequences of positive or negative dielectric anisotropies or have dielectric anisotropy that is electric field dependent.
  2. 2. Copolymers as claimed in Claim 1 which have externally variable conduction and optical properties arising from the application of an external electric or magnetic field when the polymer is in a liquid crystal phase.
  3. 3. Copolymers as claimed in Claim 1 which have externally variable conduction and optical properties arising from the application of a focused laser beam while simultaneously applying an electric or magnetic field.
  4. 4. Copolymers as claimed in Claims 1,2 or 3 which have pendant mesogenic side groups with positive dielectric anisotropy that align parallel to an applied electric field and mesogenic side groups with a negative dielectric anisotropy that align perpendicular to an applied electric field.
  5. 5. Copolymers as claimed in Claims 1,2 or 3 which have mesogenic side group molecules with frequency dependent dielectric anisotropy that align either parallel or perpendicular to the applied electric field depending upon its frequency.
  6. 6. Copolymers as claimed in any previous claim, wherein the various alignments of the pendant mesogenic side groups apply torque to the polymer backbone and interrupt the conjugation of the polymer.
  7. 7. Copolymers as claimed in any previous claim, wherein the various alignments of the pendant mesogenic side groups increase the conjugation of the polymer.
GB9901801A 1999-01-28 1999-01-28 Conducting polymers with switchable magnetic/electronic properties Expired - Fee Related GB2346148B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9901801A GB2346148B (en) 1999-01-28 1999-01-28 Conducting polymers with switchable magnetic/electronic properties

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Application Number Priority Date Filing Date Title
GB9901801A GB2346148B (en) 1999-01-28 1999-01-28 Conducting polymers with switchable magnetic/electronic properties

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GB9901801D0 GB9901801D0 (en) 1999-03-17
GB2346148A true GB2346148A (en) 2000-08-02
GB2346148B GB2346148B (en) 2002-06-19

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003079400A2 (en) * 2002-03-15 2003-09-25 Koninklijke Philips Electronics N.V. Electronic device, method, monomer and polymer
JP2014234357A (en) * 2013-05-31 2014-12-15 Dic株式会社 Compound, liquid crystal composition, and display element
CN104774621A (en) * 2014-01-15 2015-07-15 江苏和成显示科技股份有限公司 Negative liquid crystal compound and composition comprising same and application thereof
CN104974766A (en) * 2014-04-09 2015-10-14 江苏和成显示科技股份有限公司 High-clearing-point and high-refractive-index anisotropic negative liquid crystal composition and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2304723A (en) * 1995-09-05 1997-03-26 Peter Jonathan Samuel Foot Liquid-crystalline conducting polymers
GB2318119A (en) * 1996-08-20 1998-04-15 Peter Jonathan Samuel Foot Laser processed conducting polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2304723A (en) * 1995-09-05 1997-03-26 Peter Jonathan Samuel Foot Liquid-crystalline conducting polymers
GB2318119A (en) * 1996-08-20 1998-04-15 Peter Jonathan Samuel Foot Laser processed conducting polymers

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003079400A2 (en) * 2002-03-15 2003-09-25 Koninklijke Philips Electronics N.V. Electronic device, method, monomer and polymer
WO2003079400A3 (en) * 2002-03-15 2003-11-27 Koninkl Philips Electronics Nv Electronic device, method, monomer and polymer
JP2005521240A (en) * 2002-03-15 2005-07-14 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 Electronic devices, methods, monomers, and polymers
JP2014234357A (en) * 2013-05-31 2014-12-15 Dic株式会社 Compound, liquid crystal composition, and display element
CN104774621A (en) * 2014-01-15 2015-07-15 江苏和成显示科技股份有限公司 Negative liquid crystal compound and composition comprising same and application thereof
CN104774621B (en) * 2014-01-15 2017-07-28 江苏和成显示科技股份有限公司 Negative liquid crystal compound and the composition comprising the liquid-crystal compounds and its application
CN104974766A (en) * 2014-04-09 2015-10-14 江苏和成显示科技股份有限公司 High-clearing-point and high-refractive-index anisotropic negative liquid crystal composition and application thereof
CN104974766B (en) * 2014-04-09 2017-04-12 江苏和成显示科技股份有限公司 High-clearing-point and high-refractive-index anisotropic negative liquid crystal composition and application thereof

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GB9901801D0 (en) 1999-03-17
GB2346148B (en) 2002-06-19

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Effective date: 20100128