WO2012126570A1 - Composés pour un milieu cristallin liquide et leur utilisation pour des composants haute fréquence - Google Patents

Composés pour un milieu cristallin liquide et leur utilisation pour des composants haute fréquence Download PDF

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WO2012126570A1
WO2012126570A1 PCT/EP2012/000964 EP2012000964W WO2012126570A1 WO 2012126570 A1 WO2012126570 A1 WO 2012126570A1 EP 2012000964 W EP2012000964 W EP 2012000964W WO 2012126570 A1 WO2012126570 A1 WO 2012126570A1
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compounds
independently
formula
atoms
alkyl
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PCT/EP2012/000964
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German (de)
English (en)
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Christian Jasper
Atsutaka Manabe
Detlef Pauluth
Volker Reiffenrath
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Merck Patent Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
    • C07D237/30—Phthalazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
    • C09K19/3447—Pyridine condensed or bridged with another ring system, e.g. quinoline or acridine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3455—Pyridazine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
    • H01Q1/364—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q21/00—Antenna arrays or systems
    • H01Q21/06—Arrays of individually energised antenna units similarly polarised and spaced apart
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C09K2019/325—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring containing a tetrahydronaphthalene, e.g. -2,6-diyl (tetralin)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/11—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the High Frequency technical field

Definitions

  • the present invention relates to compounds having at least one bicyclic or tricyclic ring system, which with acetylene or
  • Liquid-crystalline media are used, for example, for phase shifting microwaves for tunable 'phased-array' antennas.
  • Liquid-crystalline media have long been in electro-optical
  • Displays Liquid Crystal Displays - LCDs used to display information.
  • liquid crystalline components proposed. Compounds having a (difluoro) ethylene bridge between two rings are not disclosed therein. Lately, however, liquid-crystalline media for the
  • liquid-crystalline media in high-frequency technology is based on their property that they can be controlled by a variable voltage in their dielectric properties, especially for the gigahertz range. Thus can be tuned
  • EP 2 073 290 A1 also mentions the following compounds:
  • compositions or individual compounds are generally associated with disadvantages. Most of them, among other deficiencies, lead to unfavorably high losses and / or inadequate phase shifts or material quality.
  • liquid-crystalline media For use in high-frequency technology, liquid-crystalline media with special, hitherto unusual, unusual properties or combinations of properties are needed.
  • new components for liquid-crystalline media are with
  • Tunable antennas also require liquid crystalline media with fast response time to a changed voltage between the electrodes of the cell.
  • the invention relates to compounds of the formula I,
  • non-adjacent -CH 2 - may be replaced by X, and R 3 is defined as R 1 ,
  • trans-1 4-cyclohexylene or cyclohexenylene, in which also one or two non-adjacent Ch 1 groups may be replaced by -O- and / or -S- and in which H may be replaced by F,
  • e) a radical from the group, 4-bicyclo (2,2,2) octyl, cyclobutane-1, 3-diyl, spiro [3.3] heptane-2,6-diyl, thiophene-2,5-diyl, thiophene 2,4-diyl, furan-2,5-diyl, furan-2,4-diyl, and in which groups a), b), c), d) and e)
  • C 10 alkyl or alkoxy group may be replaced, and wherein
  • At least one radical from A 2 , A 3 and A 4 represents a radical according to a
  • Y 1 , Y 2 independently of one another, are H, F, Cl, C 1 -C 10 -alkyl, preferably H or F, particularly preferably F,
  • Z 1 , Z 5 are independently a single bond
  • -C C-
  • P 1 or 2 and m, n are independently 0, 1 or 2
  • R 1 - (A 1 -Z) m -A 2 - or -A - (Z 5 -A 5 ) n -R 2 independently optionally also a radical of the formulas
  • Preferred compounds of the formula I are those in which the
  • R 1 and R 2 are both CH 3 , both F or both CF3, are not included.
  • the compounds according to the invention have a high clearing point, a low melting point and a high optical anisotropy ( ⁇ ). The unwanted rotation of the compounds is limited so that they are particularly suitable for use in the gigahertz range.
  • the relatively low loss factor in the microwave spectrum is advantageousously, the relatively low loss factor in the microwave spectrum.
  • the compounds alone or in mixture with other mesogenic components have a nematic phase over a broad temperature range. These properties make them particularly suitable for use in components for high frequency engineering, especially in liquid crystal phase shifters.
  • Liquid-crystalline media according to the invention have the corresponding properties.
  • Preferred compounds of formula I are characterized by the selection of one or more of the following parameters:
  • the counter m is preferably 0 or 1, more preferably 0.
  • the counter n is preferably 0 or 1, more preferably 0.
  • m + n is preferably 0 or
  • m + n + p is preferably 1 or 2, i. the total number of ring systems in formula I is preferably 3 or 4.
  • the groups A 2 , A 3 and A 4 preferably comprise a total of one or two bicyclic or tricyclic ring groups according to definition a). Particularly preferably, the group A 3 is a ring group according to definition a).
  • Ring groups A 2 and A 4 , and A 1 and A 5, if present, are particularly preferably an optionally substituted ring group according to definition b) or c), in particular optionally substituted 1,4-phenylene.
  • these groups support a high ⁇ value and good phase properties.
  • Y 1 / Y 2 are preferably H / F, F / H, F / F, Cl / F, CH 3 / F, F / CH 3 or F / Cl and more preferably F / F.
  • radicals R 1 or R 2 preferably R 1 , preferably denotes a straight-chain alkyl radical having 1 to 15, in particular 2 to
  • R 1 and R 2 are particularly preferably both an alkyl radical having 2 to 7 C atoms.
  • R 1 and R 2 are, for example, propyl and hexyl or butyl and butyl, furthermore propyl and pentyl, propyl and hexyl or butyl and pentyl.
  • R 1 and R 2 are, for example, propyl and hexyl or butyl and butyl, furthermore propyl and pentyl, propyl and hexyl or butyl and pentyl.
  • Group R 2 is a polar group (radical X).
  • the group R 2 X is F, Cl, Br, CN, CF 3 , OCF 3 , SCN, NCS, SF 5 or another
  • R 2 is F, CF 3 or OCF 3 .
  • the corresponding compounds of the formula I have a clearly positive dielectric anisotropy ( ⁇ ).
  • the ⁇ value is preferably 3 or more.
  • Rin groups according to definition b) preferably have the substructure Preferred embodiments of the invention are therefore represented by the following exemplary structures:
  • alkyl radical having 2 to 7 carbon atoms for example a propyl radical and the other group is a hexyl radical or both groups simultaneously a propyl, butyl, pentyl or hexyl radical.
  • the compounds of formula I can be advantageously prepared as shown in the following exemplary synthetic schemes (Scheme 1, 2).
  • the symmetrical compounds of the formula I can be prepared by means of a simple Sonogashira reaction (Scheme 1):
  • Scheme 1 Synthetic scheme for the preparation of compounds of the formula I.
  • R 1 2 in Scheme 1 and 2 have the meaning of R as defined for formula I.
  • Schemes 1 and 2 show the synthesis of certain compounds.
  • R 2 -phenyl can be generalized to any radicals -A 2 - (Z 1 -A 1 ) m -R 1 or -A 4 - (Z 5 -A 5 ) n -R 2 according to formula I.
  • the parameters R 1 2 , A 1 "5 , Z 1/5 , m and n are defined therein as above and below.
  • the liquid-crystalline media according to the present invention comprise one or more compounds of the formula I and optionally at least one further, preferably mesogenic compound.
  • the liquid-crystalline medium therefore preferably contains two or more compounds which preferably liquid crystalline.
  • Preferred media include the preferred compounds of formula I.
  • liquid-crystalline media are preferably selected from the compounds of the formula II:
  • R 11 and R 12 are independently of each other unfluorinated alkyl or
  • unfluorinated alkoxy having 1 to 17, preferably 3 to 10, C atoms or unfluorinated alkenyl, unfluorinated alkynyl, unfluorinated alkenyloxy, or unfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated alkenyl,
  • X 11 and X 12 independently of one another are F, Cl, Br, -CN, -NCS, -SCN,
  • L is independently branched or unbranched alkyl, alkenyl or alkynyl having 1 to 12 C atoms, wherein independently of one another also one or more
  • "-CH 2 -" - groups may be replaced by O, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl, fluorinated alkyl or alkenyl, fluorinated alkyloxy or alkenyloxy,
  • the liquid-crystalline media comprise one or more compounds of the formula I and one or more compounds of the formula II.
  • the liquid-crystalline media preferably contain a total of 5 to 95%, preferably 10 to 90% and particularly preferably 15 to 80%, of compounds of the formula I.
  • the liquid-crystalline media according to the present invention contain compounds selected from the group of the compounds of formulas I and II, more preferably they are predominantly, even more preferably they are substantially and quite preferably they consist entirely thereof.
  • compositions that the entity in question, i. the medium or component, the specified component or components or compound or compounds, preferably in a total concentration of 10% or more, and more preferably 20% or more.
  • “Predominantly” in this context means that the entity in question contains 55% or more, preferably 60% or more and most preferably 70% or more of the indicated component or components or compound or compounds.
  • “Substantially” in this context means that the entity in question contains 80% or more, preferably 90% or more, and most preferably 95% or more of the stated component or components or compound or compounds.
  • “Complete” in this context means that the entity in question contains 98% or more, preferably 99% or more and most preferably 100.0% of the indicated component or components or compound or compounds.
  • the liquid-crystalline media preferably contain a total of 10 to 100%, preferably 20 to 95% and particularly preferably 25 to 90%, of compounds of the formulas I and II.
  • the compounds of formula II preferably become stronger in a total concentration of 10% to 90% preferably from 15% to 85%, even more preferably from 25% to 80% and most preferably from 30% to 75% of the total mixture.
  • the liquid-crystalline media may also contain other additives such as stabilizers, chiral dopants and nanoparticles.
  • the individual compounds added are used in concentrations of 0.005 to 6%, preferably from 0.1 to 3%.
  • the total concentration of these other ingredients is in the range of 0% to 10%, preferably 0.1% to 6%, based on the total mixture.
  • concentration data of the other constituents of the liquid-crystal mixtures, ie the liquid-crystalline or mesogenic compounds are taken into account without taking into account the concentration of these
  • the liquid-crystalline media preferably contain 0 to 10% by weight, in particular 0.01 to 5% by weight and more preferably 0.1 to 3% by weight, of stabilizers.
  • the media preferably contain one or more stabilizers selected from 2,6-di-tert-butylphenols, 2,2,6,6-tetramethylpiperidines or 2-benzotriazol-2-yl-phenols. These adjuvants are known in the art and commercially available, for. B. as
  • An embodiment of the invention is therefore also a process for the preparation of a liquid-crystal medium, which is characterized in that one or more compounds of the formula I is mixed with one or more further compounds and optionally with one or more additives.
  • the further compounds are preferably selected from the compounds of the formula II, as indicated above, and optionally one or more further compounds.
  • dielectrically positive describes compounds or components with ⁇ > 3.0, dielectrically neutral with -1.5 ⁇ 3.0 and dielectrically negative with ⁇ ⁇ -1.5.
  • the dielectric anisotropy of each compound becomes apparent from the results of a solution of 10% of each individual compound in one
  • the applied voltage is a square wave with a frequency of 1 kHz and an effective value of typically 0.5V to 1.0V, but is always chosen to be below the capacitive threshold for the particular test mixture. is defined as / 3.
  • Constants of the compounds are determined from the change in the respective values of the host mixture upon addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%.
  • threshold voltage refers to in the present
  • V 0 In the optical threshold and are given for 10% relative contrast (V 0 ), the term saturation voltage refers to optical saturation and is given for 90% relative contrast (V 90 ), in both cases, unless expressly stated otherwise.
  • the optical anisotropy ( ⁇ ) is at a wavelength of 589
  • the dielectric anisotropy ( ⁇ ) is determined at a frequency of 1 kHz
  • Test cells manufactured at Merck KGaA, Germany.
  • the test cells for the determination of ⁇ have a layer thickness of about 20 pm.
  • the electrode is a circular ITO electrode with a surface area of 1.13 cm 2 and a guard ring.
  • the alignment layers are SE-1211 from Nissan
  • Capacitance is determined using a Solatron 1260 frequency response analyzer using a sine wave with a voltage of 0.3 Vrms.
  • the light used in the electro-optical measurements is white light.
  • a structure with a commercially available device DMS Fa. Autronic Melchers, Germany is used. The characteristic stresses are below vertical
  • the threshold voltage ( ⁇ o), mid-gray voltage (V 50 ) and saturation voltage (V 90 ) are determined for 10%, 50% and 90% relative contrast, respectively.
  • the liquid-crystalline media are investigated for their properties in the frequency range of microwaves as in A. Penirschke et al. "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz ", 34 European Microwave Conference - Amsterdam, pp. 545-548 See also A. Gaebler et al.," Direct Simulation of Material Permittivities 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), p 463-467 and DE 10 2004 029 429 A, in which a measuring method is also described in detail.
  • the liquid crystal is filled in a capillary made of polytetrafluoroethylene (PTFE) or quartz glass.
  • the capillary has an inner radius of 180 ⁇ and an outer radius of 350 ⁇ .
  • the effective length is 2.0 cm.
  • the filled capillary is placed in the center of the cylindrical cavity with a resonant frequency of 19 GHz.
  • This cavity has a length of 11, 5 mm and a radius of 6 mm.
  • the dielectric constant and the loss angle at the corresponding target frequency are calculated by means of equations 10 and 11 of FIG previously mentioned document A. Penirschke et al, 34 th European Microwave Conference -. Amsterdam, pp 545-548 determined as described there.
  • the values for the components of the properties perpendicular to and parallel to the director of the liquid crystal are obtained by orienting the liquid crystal in a magnetic field.
  • the magnetic field of a permanent magnet is used.
  • the strength of the magnetic field is 0.35 Tesla.
  • the orientation of the magnet is adjusted accordingly and then rotated accordingly by 90 °.
  • the dielectric anisotropy in the ⁇ -wave range is defined as
  • the material quality ( ⁇ ) is defined as with the maximum dielectric loss factor tan
  • the material quality ( ⁇ ) of the preferred liquid crystal materials is 6 or more, preferably 7 or more, preferably 10 or more, preferably 15 or more, more preferably 25 or more and most preferably 30 or more.
  • the preferred liquid crystal materials have in the respective components phase shifts of 157 dB or more, preferably 207 dB or more, preferably 307 dB or more, preferably 407 dB or more, preferably 507 dB or more, more preferably 807 dB or more and most preferably 1007 dB or more.
  • liquid-crystal media according to the invention are preferred.
  • nematic phases of at least from -20 ° C to 80 ° C, preferably from -30 ° C to 85 ° C and most preferably from -40 ° C to 100 ° C on.
  • the phase is up to 120 ° C or more, preferably up to 140 ° C or more, and most preferably up to 180 ° C or more.
  • nematic phase means, on the one hand, that no smectic phase and no crystallization are observed at low temperatures at the corresponding temperature and, on the other hand, that clarification does not yet occur on heating from the nematic phase.
  • the investigation at low temperatures is carried out in a flow viscometer at the appropriate temperature and checked by storage in test cells, with a layer thickness of 5 pm, for at least 100 hours.
  • the clearing point is measured in capillaries by conventional methods.
  • the liquid crystal media according to the present invention preferably have a clearing point of 90 ° C or more, more preferably 100 ° C or more, even more preferably 120 ° C or more, more preferably 150 ° C or more, and most preferably 170 ° C or more, up.
  • the ⁇ of the liquid crystal medium according to the invention at 1 kHz and 20 ° C is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more.
  • the ⁇ of the liquid crystal media according to the present invention is preferably 589 nm (Na D ) and 20 ° C in the range of 0.20 or more to 0.90 or less, more preferably in the range of 0.25 or more to 0.90 or less, more preferably in the range of 0.30 or more to 0.85 or less and most preferably in the range of 0.35 or more to 0.80 or less.
  • the ⁇ of the liquid crystal media according to the present invention is preferably 0.50 or more, more preferably 0.55 or more.
  • the liquid-crystal media according to the invention are characterized by high anisotropies in the microwave range.
  • the birefringence is e.g. at about 8.3 GHz preferably 0.14 or more, more preferably 0.15 or more, more preferably 0.20 or more, more preferably 0.25 or more, and most preferably 0.30 or more.
  • the birefringence is preferably 0.80 or less.
  • the liquid crystals used are either individual substances or mixtures. Preferably, they have a nematic phase.
  • the term compounds means both one compound and several compounds.
  • Preferred devices containing a liquid crystal medium or at least one compound according to the invention are phase shifters, varactors, antenna arrays (eg for radio, mobile radio, radio,
  • Microwaves / radar and other data transmission Microwaves / radar and other data transmission), matching circuit adaptive filters and others. Preference is given to components for the
  • High frequency technology as defined above. Preference is also given by different applied electrical voltages modulatable components. Very particularly preferred components are tunable
  • phase shifter In preferred embodiments, multiple phase shifters are operatively connected, resulting in, for example, a phased array antenna, commonly referred to as a 'phased array' antenna.
  • a group antenna uses the
  • Phase shifting of the arranged in a matrix transmitting or receiving elements to achieve by bundling interference From a row or grid-like parallel arrangement of
  • Phase shifters can be a so-called 'phased array' build, which can be used as a tunable or passive transmitting or receiving antenna for
  • Preferred applications are radar installations and
  • a liquid-crystalline medium according to the invention is typically introduced into rectangular cavities of less than 1 mm thickness, several mm wide and several centimeters long.
  • the cavities have opposing electrodes mounted along two long sides.
  • Such arrangements are familiar to the skilled person.
  • halogen or halogenated stands for F, Cl, Br and I, especially for F and Cl and especially for F.
  • alkyl preferably includes straight-chain and branched alkyl groups having 1 to 15 carbon atoms, in particular the
  • alkenyl preferably comprises straight-chain and branched alkenyl groups having 2 to 15 carbon atoms, in particular the straight-chain groups.
  • Particularly preferred alkenyl groups are C 2 to C 7 -1 E-alkenyl, C 4 to C 7 -3E-alkenyl, C 5 to C 7 -4-alkenyl, C 6 to C 7 -5-alkenyl and C 7 -6-alkenyl Alkenyl, in particular C 2 to C 7 -1 E-alkenyl, C to C 7 - 3E-alkenyl and C 5 to C 7 -4 alkenyl.
  • alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups of up to 5 carbon atoms are generally preferred.
  • alkoxy preferably includes straight-chain radicals of
  • N is preferably 1 to 6.
  • Preferred alkoxy groups are, for example, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy.
  • oxaalkyl or “alkoxyalkyl” preferably encompasses straight-chain radicals of the formula C n H2 wherein n and m are each independently from 1 to 10 n + i-0- (CH2) m. Preferably, n is 1 and m is 1 until 6.
  • fluorinated alkyl preferably includes mono- or polyfluorinated radicals. Perfluorinated radicals are included.
  • fluorinated alkoxy includes mono- or polyfluorinated radicals. Perfluorinated radicals are preferred. Particularly preferred is the radical OCF 3 .
  • Groups preferably substituted by -O- refers to those groups in which a non-terminal CH 2 group is replaced OH groups are included in the general meaning with The term” substituted cycloalkyl "includes one or more times alkyl-substituted cycloalkyl, especially alkyl of 1 to 8
  • substituted phenyl includes phenyl which is monosubstituted or polysubstituted by a group such as R 1 , in particular phenyl which is substituted by F, Cl, alkyl or alkoxy.
  • Applications with frequencies in the range of 1 MHz to 10 THz preferably from 1 GHz to 3 THz, more preferably 2 GHz to 1 THz, particularly preferably from 5 to 300 GHz.
  • the application is preferably in the microwave spectrum or adjacent, for the
  • the liquid-crystal media according to the invention consist of one or more compounds, preferably from 2 to 30, more preferably from 3 to 20 and most preferably from 3 to 16 compounds.
  • Dissolved compound in the compound used in the larger amount If the temperature is above the clearing point of the compound used in the higher concentration, the completion of the dissolution process is particularly easy to observe.
  • the media in other conventional ways, for example using so-called premixes, which may for example be homologous or eutectic mixtures of compounds, or using so-called “multi-bottle” systems, whose constituents are themselves ready-to-use mixtures.
  • acetylenes and boronic acids used are commercially available or can be prepared analogously to known syntheses which are known to the person skilled in the art.
  • the radicals "C4H9” stand for unbranched n-butyl radicals. The same applies to C3H7, C6H13, etc.
  • Residue is purified by column chromatography (S1O2, toluene -> toluene
  • Washed sodium bicarbonate solution dried over sodium sulfate, filtered off and concentrated on a rotary evaporator.
  • Residue is purified by column chromatography (S1O2, dichloromethane); the product is obtained as a yellow oil.
  • the formulation is heated to -20 ° C, with 500 mg (0.55 mmol) tris (dibenzylideneaceton) dipalladium, 160 mg (0.39 mmol) 2-dicyclohexylphosphino-2 '-6' -dimethoxybiphenyl and 8.5 g (19 mmol) of the triflate obtained in the previous reaction in 50 ml of tetrahydrofuran and refluxed for 16 h.
  • the further purification is carried out by recrystallization from isopropanol and ethanol-toluene mixtures.
  • a liquid crystal medium M-1 having the composition and properties as shown in the following table is prepared.
  • the compound (2) (No. 15) is from Synthesis Example 2.
  • phase shifters for 'phased array' antennas.
  • a medium C-1 without the component (2) is prepared from the compounds Nos. 1-14 of the medium M-1, wherein the
  • a liquid-crystal medium M-2 having the composition of M-1 is prepared, except that the compound (7) of Synthesis Example 7 is used instead of the compound (2).
  • controllability ⁇ , the maximum loss factor (here tan ⁇ ⁇ , r JL ) and the material quality ⁇ are each significantly improved compared to the comparison mixture C-1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des composés comprenant au moins un système bi ou tricyclique, qui est lié par des ponts acétylène ou difluoroéthylène, et leur utilisation pour des composants haute fréquence, des milieux cristallins liquides contenant ces composés et des composants haute fréquence contenant ces milieux, notamment des antennes, en particulier pour la gamme gigahertz. Ces milieux cristallins liquides peuvent par exemple servir au déphasage d'ondes hyperfréquence dans des antennes accordables à commande de phase.
PCT/EP2012/000964 2011-03-22 2012-03-03 Composés pour un milieu cristallin liquide et leur utilisation pour des composants haute fréquence WO2012126570A1 (fr)

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WO2016199528A1 (fr) * 2015-06-08 2016-12-15 Jnc株式会社 Composé de cristaux liquides contenant du benzothiophène, composition de cristaux liquides et élément d'affichage à cristaux liquides
US10100252B2 (en) 2016-06-15 2018-10-16 Jnc Corporation Liquid crystal composition and liquid crystal display device
EP3363795A4 (fr) * 2015-10-13 2019-10-09 JNC Corporation Composé à cristaux liquides présentant du benzothiophène, composition à cristaux liquides et élément d'affichage à cristaux liquides
CN111183137A (zh) * 2017-10-19 2020-05-19 默克专利股份有限公司 二苯并呋喃和二苯并噻吩

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CN112851562A (zh) * 2021-01-22 2021-05-28 烟台显华化工科技有限公司 一种芳香环液晶化合物及其液晶组合物和应用
EP4332198A1 (fr) * 2022-08-29 2024-03-06 Merck Patent GmbH Composés hétérocycliques pour cristaux liquides

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WO2016199528A1 (fr) * 2015-06-08 2016-12-15 Jnc株式会社 Composé de cristaux liquides contenant du benzothiophène, composition de cristaux liquides et élément d'affichage à cristaux liquides
JPWO2016199528A1 (ja) * 2015-06-08 2018-01-25 Jnc株式会社 ベンゾチオフェンを有する液晶性化合物、液晶組成物および液晶表示素子
US10563126B2 (en) 2015-06-08 2020-02-18 Jnc Corporation Liquid crystal compound having benzothiophene, liquid crystal composition and liquid crystal display device
EP3363795A4 (fr) * 2015-10-13 2019-10-09 JNC Corporation Composé à cristaux liquides présentant du benzothiophène, composition à cristaux liquides et élément d'affichage à cristaux liquides
US10100252B2 (en) 2016-06-15 2018-10-16 Jnc Corporation Liquid crystal composition and liquid crystal display device
CN111183137A (zh) * 2017-10-19 2020-05-19 默克专利股份有限公司 二苯并呋喃和二苯并噻吩
JP2020537674A (ja) * 2017-10-19 2020-12-24 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ ジベンゾフランおよびジベンゾチオフェン
JP7230018B2 (ja) 2017-10-19 2023-02-28 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング ジベンゾフランおよびジベンゾチオフェン
CN111183137B (zh) * 2017-10-19 2023-05-16 默克专利股份有限公司 二苯并呋喃和二苯并噻吩

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