Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
  • C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
  • C07C65/26—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic containing rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
  • C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
  • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
• • 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
  • C08G73/00—Macromolecular 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
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide

Definitions

• the invention relates to chain-shaped polycyclic bisanhydrides and polyimides which can be obtained by polycondensation of the chain-shaped polycyclic bisanhydrides with diamines.
• LCDs Liquid crystal displays
• Examples include wristwatches, notebook computers, TV sets and display displays in the instrument panel of motor vehicles or in the aircraft cockpit.
• a liquid crystal display consists of a liquid crystalline layer with opposite sides, a set of electrodes on each side of the liquid crystalline layer and a polymeric orientation layer between each set of electrodes and the liquid crystalline layer.
• the liquid-crystalline molecules are oriented at a certain angle, which is referred to as the angle of inclination, with respect to the plane of the inside of the two substrates, for example
• the inside of the substrates have a coating of sets of transparent electrodes (electrical conductors), usually of indium tin oxide.
• the orientation process is carried out by applying the organic polymer from solution to the two substrates coated with indium tin oxide. After removal of the solvents and / or curing of the polymer layers, the substrate surfaces are usually rubbed or polished in a certain direction with fabric. The rubbing or polishing serves to produce a uniform optical direction. After polishing the two substrates, they are rotated by 70 to 360 ° to one another, connected to one another with suitable spacers and using organic adhesives, and filled with a wide variety of mixtures of liquid-crystalline materials. At this stage of the manufacturing process, polarizing films are often applied to the outer substrate surfaces by lamination. Finally, the electrical connections to both substrates are made.
• Polyimide films are the most commonly used orientation films today. Polyimide films are used to control the orientation and the
• Tilt angle of the liquid crystal molecules in liquid crystal displays are very thin, their thickness is generally between 100 and 2000 A. Orientation in a single direction is induced by polishing with special textile materials. The actual angle of inclination is determined as a function of the order of the polymers on the surface of the resulting surface energy, the type of fabric used to polish the surface, and the size of the work involved in polishing.
• the object of the invention is to provide new polyimide materials which are suitable for producing polymeric orientation films in liquid crystal displays.
• chain-shaped polycyclic bisanhydrides containing 2 to 12 chain cycles, selected from 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, bicyclopentylene, Bicyclooctylene, cubylene, which can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy, the cycles being bridged by groups selected from a single bond, -CF 2 O-, -OCF 2 - , -O-, -S-, -SO 2 -, -CO-, -NH-, - (CH 2 ) ⁇ - ⁇ o-, - (CF 2 ) ⁇ - ⁇ o-.
• Preferred chain-shaped polycyclic bisanhydrides are those of the general formula (I):
• A, B, C and D can be the same or different and 1, 3-phenylene, 1, 4-phenylene, 2,6-naphthylene, 2,7-naphthylene and 1, 4-cyclohexylene with halogen, cyano, alkyl , Fluoroalkyl, alkoxy and / or fluoroalkoxy can be substituted one or more times,
• E and F can be the same or different and
• w, x, y and z are independently 0 or 1.
• Preferred groups Z are a single bond - CF 2 O-, -OCF ⁇ -, -CO-, -CH 2 -, -CH 2 CH 2 - ( -O-, -S-, -SO 2 -, -CF 2 CF. 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -,
• Particularly preferred chain-shaped polycyclic bisanhydrides are those with a symmetrical structure of the general formula (II) - (V):
• A, B are as defined above, z 1 , z- 1 , z 2 , z- 2 , z 3 have the meaning of Z 1 - Z 5 as defined above with the proviso that
• Z2, Z - 3 are as defined above.
• an aromatic halide is first converted into a Grignard compound or into a lithiated compound and then converted into the dithiocarboxylic acid with carbon disulfide.
• the dithiocarboxylic acid is converted into a thioester with a phenol in the presence of an alkali metal hydride and iodine.
• the desired -O-CF 2 bridge is then formed from the thioester using a fluorinating agent.
• a cyclohexanone is first reacted with hexamethylphosphoric triamide and dibromodifluoromethane, a difluorohexylidene derivative being obtained.
• Bromine is first added to this and then etherified by reaction with a phenolate with simultaneous elimination of hydrogen bromide to form a —CF 2 —O bridge.
• a bis (alkylthio) carbenium salt is first reacted in the presence of a base with a compound having at least one hydroxyl group and then, preferably in situ, with a fluorinating agent and an oxidizing agent for connection to at least one -CF 2 - O-bridge in the molecule is oxidatively fluorinated.
• the bis (alkylthio) carbenium salts can be prepared very easily from the corresponding carboxylic acids or activated carboxylic acid derivatives.
• Suitable carboxylic acid derivatives are, for example, halides, carboxylic acid pseudohalides, carboxylic acid sulfonylates, which are suitably substituted, for example a trifluoromethanesulfonylate.
• Carboxylic anhydrides and alkyl or phenyl carboxylic acid esters can also be used. The salts precipitate out of the reaction solution in a clean form and can be used in the next stage without further purification.
• the bis (alkylthio) carbenium salt is first converted to the dithioorthoester by reaction with the compound containing at least one hydroxyl group.
• This dithioorthoester is generally not isolated, but is immediately implemented further.
• the oxidative fluorination to give a compound containing a -CF 2 -O group takes place under very mild, slightly basic conditions and, in contrast to conventional methods, is therefore compatible with a large number of unprotected functional groups, for example a nitrile group.
• a further advantage is that the stereochemistry of the radicals, for example an ice or trans-cyclohexylene radical, is retained in the reaction.
• the basic steps are summarized in Figure 1 below.
• the carboxylic acid derivative A in which X represents, for example, -OH, halogen, pseudohalogen, substituted sulfonate, an anhydride, alkoxy or phenoxy, is reacted with an alkylthiol to form the bis (alkylthio) carbenium salt B.
• Dithiols which lead to the formation of a cyclic cation are preferably used.
• Ethanedithiol, propanedithiol or 1,2-benzenedithiol, which lead to the formation of dithianylium or dithiolanylium salts, are therefore particularly suitable.
• This salt B is then converted to the orthoester C using a hydroxy compound R b -OH.
• the orthoester C is generally not isolated, but directly oxidatively to Compound D implemented.
• the method can be used universally, so that R a and R b are not subject to any restrictions.
• R a and R b can thus be, for example, independently of one another an alkyl, an aryl, a cycloalkyl or an alkenyl radical, where these radicals can in turn be substituted as desired, for example by halogen, pseudohalogen, hydroxyl or carbonyl groups.
• the present invention further relates to polyimides having -CF 2 O groups, which are obtainable by polycondensation of chain-shaped polycyelic bisanhydrides according to the invention and optionally further polycyelic bisanhydrides with diamines.
• Suitable diamines are the diamines of the following formulas (VII) (XXXVI):
• Preferred diamines are chain polycyelic diamines which are terminated at the chain ends by -NH 2 .
• Particularly preferred diamines contain 2 to 12 chain cycles selected from 1, 3-phenylene, 1, 4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1, 4-cyclohexylene, bicyclopentylene, bicyclooctylene and cubylene, which with Halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy can be substituted one or more times, the cycles being selected by bridging groups from a single bond, -CF 2 O-, -OCF 2 -, -O-, -S-, -SO 2 -, -CO-, -NH-, - (CH 2 ) ⁇ - ⁇ o-, - (CF 2 ) 1-10 -, -CH (CH 3 ) -, -CH (CCI 3 ) -, - CH (CF 3 ) -, -C (CH 3 ) 2 -, -C (CF 3
• A, B, C and D may be the same or different and 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, bicyclopentylene, bicyclooctylene and cubylene, the can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy,
• -NH 2 is independently bound in the 3- or 4-position
• w, x, y and z are independently 0 or 1.
• Examples are diamines of the general formulas (XXXVI) to (XL)
• A, B are as defined above,
• T ⁇ z 3 have the meaning of Z 1 - Z 5 as defined above with the proviso that
• the present invention furthermore relates to polyimides which are obtained by polycondensation of chain-shaped polycyelic bisanhydrides and / or further polycyelic bisanhydrides with chain-shaped polycyclic diamines which are terminated by -NH 2 at the chain ends are terminated and at least one bridging group selected from - CF 2 O- or -OCF 2 - are available.
• the diamines can be constructed analogously to the diamines of the general formulas (XXXVI) to (XL) with the additional proviso that at least one bridging group in the diamines is -CF2O- or -OCF 2 -.
• Suitable further bisanhydrides are the compounds of the formulas (XLI) to (LVIII):
• the monomers mentioned are notable for very good solubility in the customary organic solvents.
• the size of the repetitive units lowers the relative number of link positions (imide bonds). These linking positions can contribute to the binding of ionic impurities to the polymer and thus impair the usability of the polymer as a component of electronic components, for example by reducing the electrical resistance.
• the reduction in the number of linking positions based on the molecular weight is therefore a decisive advantage.
• polyimides according to the invention are furthermore their high thermal, photochemical and chemical stability, their high lipophilicity, their high electrical resistance and their low affinity for ionic impurities. These properties offer particular advantages when the polyimides are used in electronic components, for example as an orientation material in LCDs or organic light-emitting diodes (OLEDs) or as an insulation material for electronic circuits.
• the polyimide orientation film can be produced by solution polymerization of essentially equimolar amounts of the bisanhydride and the diamine, preferably at room temperature to 50 ° C., for example in N-methylpyrrolidone or N, N-dimethylacetamide as solvent.
• the imide can then be formed in the polyamic acid solution obtained by chemical imidation with acetic anhydride and pyridine at 50 ° C. or by thermal imidation by heating to 70 to 250 ° C.
• the polyimide obtained can then be precipitated, filtered and dried in vacuo.
• the polyimide can then be dissolved in ⁇ -butyrolactone as a solvent and applied by spin coating to a glass plate coated with indium tin oxide and at a temperature of, for example, 150 ° C. to 220 ° C. for a period of generally one minute to two Hours imidized and dried.
• the polyimide coating obtained in this way can then be polished in a manner known per se in order to obtain the orientation-controlling film.
• Trifluoromethanesulfonic acid is heated to 120 ° C for 1 h. The mixture is allowed to cool to 80 ° C., diluted with 300 ml of acetonitrile and then diluted with 2 l of dibutyl ether. After cooling to 0 ° C., the precipitated product 2 is filtered off with suction, washed with diethyl ether and dried.
• the anhydride 5 and the diamine 4 are dissolved in NMP and stirred under nitrogen for 22 h at room temperature. The mixture is then heated to 100 ° C. for 6 h and the polymer is precipitated by adding 50% aqueous ethanol. The crude product is reprecipitated once from 20 ml and once from 30 ml of NMP by adding 50% aqueous ethanol.

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• 2001
  • 2001-06-19 DE DE10129335A patent/DE10129335A1/de not_active Withdrawn
• 2002
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