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WO1990012831A1 - Matieres polymeres ramifiees a orientation dipolaire - Google Patents

Matieres polymeres ramifiees a orientation dipolaire Download PDF

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Publication number
WO1990012831A1
WO1990012831A1 PCT/EP1990/000546 EP9000546W WO9012831A1 WO 1990012831 A1 WO1990012831 A1 WO 1990012831A1 EP 9000546 W EP9000546 W EP 9000546W WO 9012831 A1 WO9012831 A1 WO 9012831A1
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WIPO (PCT)
Prior art keywords
polymer materials
monomers
acceptor
polymer
dipolar
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PCT/EP1990/000546
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German (de)
English (en)
Inventor
Dieter Dorsch
Eike Poetsch
Bernhard Rieger
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Merck Patent GmbH
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Merck Patent GmbH
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Publication of WO1990012831A1 publication Critical patent/WO1990012831A1/fr
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • 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
    • C08G73/18—Polybenzimidazoles
    • 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
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers
    • G02F1/3616—Organic materials containing polymers having the non-linear optical group in the main chain

Definitions

  • the invention relates to polymer materials based on main chain polymers containing polar monomer units, the polar monomer units containing electron donor / acceptor-substituted conjugated ⁇ systems and being oriented in the same direction in the polymer main chains, characterized in that the main chain polymers are branched .
  • the frequency doubling (second harmonic generation, SHG) is the generation of light which has half the wavelength compared to the incident light.
  • the change in the refractive index of a material with an applied electric field is referred to as the electro-optical effect (Pockels effect); Methods of sum and difference frequency mixing as well as frequency division allow the continuous tuning of laser light.
  • Nonlinear optical materials are suitable for the production of optical components. These include, for example, electro-optical modulators, electro-optical switches, electro-optical directional couplers and frequency doublers. - 2 -
  • optical communications technology for modulation and control of optical signals
  • spatial light modulators in optical signal processing for frequency doubling 5 of semiconductor lasers
  • optical data storage for optical data storage
  • sensor technology for xerography
  • a number of inorganic substances such as Potassium dihydrogen phosphate or lithium niobate shows non-linear optical properties. All of these connections are
  • Organic compounds of the nitroaniline type are known from Garito et al., Laser Focus 1 (1982) and EP-0091 838. Their relatively good values for the photochemical However, stability and the dielectric susceptibility of the second order go hand in hand with poor crystallizability and poor mechanical stability. In particular, the production of thin layers, as required by the integrated optics, does not succeed with these materials.
  • NLO chromophores Polymers that are provided with dissolved or covalently bound NLO chromophores generally only acquire a non-linear second-order susceptibility by applying an electrical field in the fluid state, the NLO chromophores being dipolarly oriented ( ⁇ (2) ' ) • The dipolar orientation is permanently frozen by cooling below the glass temperature. ⁇ (2 ') is therefore in a first approximation proportional to the concentration of the NLO chromophores, the E-field strength, the hyperpolarizability ß and the dipole moment ⁇ . For this reason, compounds with large dipole moments and at the same time high ⁇ values are of significant interest.
  • NLO chromophores consisting of a conjugated ⁇ system with an electron acceptor or an electron donor bound to them have already been investigated.
  • Polymer materials containing such donor / acceptor substituted ⁇ systems in side chains are known, e.g. Polymethacrylates (EP 0231770, EP 0230898), polystyrenes (JP 63041831, JP 61148433) or
  • Polyester EP 0297530.
  • Polymers that contain nonlinear optical chromophores as part of the main chain have hardly been studied. Examples include polybenzimidazoles (EP 0265921) and thermotropic liquid crystal main chain polymers, in which non-linear optical chromophores are incorporated as chain links in the main chain (JP 62238538).
  • the known polymers still have unsatisfactory nonlinear optical properties, on the other hand, they do not meet the requirements for economical use as nonlinear optical media, because they have undesirably high values for the optical attenuation, for example.
  • the polymer materials according to the invention are distinguished in particular by a lower optical attenuation compared to previously known nonlinear optical polymers.
  • the invention therefore relates to polymer materials based on main chain polymers containing polar monomer units, the polar monomer units containing electron donor / acceptor-substituted conjugated ⁇ systems and being oriented in the same direction in the polymer main chains, characterized in that the main chain polymers are branched.
  • the invention furthermore relates to nonlinear optical arrangements which contain the polymer materials according to the invention.
  • the invention also relates to a method for producing the nonlinear optical arrangements according to the invention by placing the polymer materials on a. Applying the substrate and aligning it dipolar or by polarizing monomers having branching sites, optionally in a mixture with polar monomers without branching sites, both types of monomer containing electron donor / acceptor-substituted conjugated ⁇ systems, polymerized on a substrate and optionally di ⁇ polar aligns.
  • the invention finally relates to the use of the non-linear optical arrangements according to the invention in optical components, and also optical components which contain the non-linear optical arrangements according to the invention.
  • the structure of the polar monomer units in the skin chain polymers according to the invention is largely uncritical. Of importance is the presence of a conjugated ⁇ system which is substituted at one end by at least one electron donor and at the other end by at least one electron acceptor.
  • the polar monomers must be such that reactive groups are available at both ends which allow a head-to-tail linkage of the individual molecules.
  • the reactive groups can themselves be electron donor or acceptor groups or a part thereof or at least be in close proximity to the electron donor or acceptor groups, for example geminally on an aromatic system.
  • polar monomers are equally bifunctionalized at one end and thus have a branching point which can react equally at both positions with the functional group of a second monomer located at the other end of the ⁇ system. These monomers are thus trifunctionalized overall.
  • branched main chain polymers are formed with polar monomer units of the same orientation, the degree of branching being predetermined by the relative ratio of the monomers used (bi- / trifunctional) can.
  • the monomer ratio bi-: trifunctional is preferably in the range from 0: 100 to 90:10, in particular a range from 0: 100 to 70:30 is preferred.
  • X and Y represent the functional groups that react with each other, ii means the conjugated ⁇ system, which is substituted at one end by at least one electron donor and at the other end by at least one electron acceptor.
  • X and / or Y can also themselves be an electron donor or acceptor or a part thereof.
  • the arrow (- ») is intended to indicate that the monomers, branched (a) and linear (b), are polar and that the polar monomer units in the branched main chain polymers according to the invention are oriented in the same direction.
  • step I both groups Y of a monomer a reacted with one monomer a each. Of the four reactive positions (I), three reacted further in step II, namely one (IIA) with a monomer a and two (IIB) with a monomer a or b.
  • the degree of polymerization is preferably 8-1000, more preferably 10-300.
  • the degree of branching is determined on the one hand by the ratio of the starting materials a / b and on the other hand by the number of branches actually occurring, e.g. IIB / IIA.
  • Particularly preferred ⁇ systems are those in which an aromatic with a double bond or a triple bond and in which no more than two double and / or triple bonds are linked to one another.
  • Preferred aromatic systems are carbocycles and heterocycles with up to 18 ring atoms, but with no more than three Heteroatoms, preferably 1,4-phenylene, 2,6- and 2,7-naphthylene, anthracene and phenanthrene diyl, pyrroldiyl, furandiyl, thiophendiyl, imidazole diyl, pyrazole diyl, oxazole diyl, thiazole diyl, pyridinediyl, pyrimidinediyl, triaquinindinediyl , Isoquinolinediyl, quinoxalinediyl, indoldiyl, benzimidazole diyl, benzothiazole diyl.
  • An electron-rich heteroaromatic is preferably linked to the donor and an electron-poor to the acceptor.
  • Compounds in which no more than two heteroaromatics are present are particularly preferred.
  • the ⁇ system can also be a single aromatic.
  • Preferred electron donors are amino, alkoxy, alkylthio, and also alkyl, vinyl, hydroxy and thio groups.
  • nitro, cyano, alkoxycarbonyl and amide groups, halogen, and ethenylene substituted by -CN and / or -COOR, and also halogen atoms are preferred.
  • Acyl, haloalkyl and alkoxysulfonyl groups are also preferred.
  • Possible functional groups are, for example, those which are capable of polycondensation or polyaddition.
  • Preferred monomers a and b are those in which electron donor and acceptor groups are linked to aromatic carbon atoms.
  • the functional groups X and Y are then, for example, geminally linked or completely or partially identical to the donor / acceptor groups.
  • Preferred on the acceptor side are e.g. Phenyl nuclei which are substituted by an electron acceptor indicated above and in the 2- or 3-position by a group capable of polymerization or condensation. Pyridyl nuclei are still preferred. In this case the electron acceptor group is identical to the functional group. The pyridine nitrogen then reacts with poly addition. Additional electron acceptor groups may also preferably be present geminally on the phenyl and pyridyl nucleus. The rest of the conjugated ⁇ system is preferably linked para to an electron acceptor group with the ring.
  • a phenyl nucleus which carries an electron donor group mentioned above in parallel.
  • the second functional group and / or further donor groups can be in the adjacent position.
  • the second functional group can also be identical to or part of a donor group, for example a carboxyl or hydroxyl group, a halide or another suitable leaving group in one or both radicals R of a donor NR ".
  • Suitable monomers a and b are, for example, the compounds of the formula 1
  • A is a carbo- or heterocyclic aromatic system with 5 to 18 ring atoms, which can consist of C, N, O and S atoms with a total of up to three heteroatoms,
  • A is an electron acceptor group
  • D is an electron donor group
  • the new compounds of formula 1 are also the subject of the invention.
  • the functional groups X and Y must be in the form of a molecule such that X of one molecule can react with Y of a second molecule. For the sake of simplicity, this is indicated below by the formulation "X / Y”.
  • R 'de notes H or an alkyl radical having up to 6 carbon atoms.
  • OH / OH or Hal / OH in which shark is a halide such as F, Cl or Br.
  • the halide is preferably attached to the benzene nucleus in the o-position to the nitro group and can thus be substituted nucleophilically.
  • COOR '/ NR' and COOR '/ SH are also preferred.
  • the group X is preferably in the o-position to NO ⁇ , but can also be bound in the m-position.
  • the spacer means an alkylene which may be interrupted by -0- or -NR'- and has up to four carbon atoms.
  • Z1 and Z2 preferably denote a single bond,
  • -C C- or -C ⁇ C-.
  • A is preferably 1,4-phenylene, 2,6- and 2,7-naphthylene, anthracene and phenanthrenediyl, pyrroldiyl, furandiyl, thiophendiyl, imidazole diyl, pyrazole diyl, oxazole diyl, thiazole diyl, pyridinediyl, pyrimidinediyl, triazinediyl, quinolinediyl , Isoquinolinediyl, quinoxalinediyl, indoldiyl, benzimidazole diyl or benzothiazole diyl.
  • Preferred electron donors D are amino, alkoxy, alkylthio, and also alkyl, vinyl, hydroxy and thio groups.
  • nitro, cyano, alkoxycarbonyl and amide groups, halogen, and ethenylene substituted by -CN and / or -COOR, and also halogen atoms are preferred.
  • Acyl, haloalkyl and alkoxysulfonyl groups are also preferred.
  • n is preferably 0 or 1. Particular preference is given to those compounds of the formula 1 which have the given preferred meanings for X, Y, Z 1, Z2, A1, A,
  • Stilbene derivatives of Formula 1 Other suitable monomers a and b for the preparation of the polymer materials according to the invention are pyridine derivatives which are structured like the compounds of formula 1, but in which the nitrophenyl radical is replaced by a pyridin-4-yl radical. The grouping (Sp) 0 . -X is then no longer present, the pyridine nitrogen thus reacts with polyaddition with the part -RY of a second molecule.
  • Y preferably denotes a halide such as Cl, Br or I or another easily substitutable group such as mesylate or tosylate.
  • the reactive groups Br, I, mesylate and tosylate the polymerization can already partially occur in situ.
  • a functional group is therefore identical to the electron acceptor group.
  • the monomers a and b used to prepare the polymer materials according to the invention can be prepared by standard processes in organic chemistry.
  • reaction conditions can be found in the standard works of preparative organic chemistry, for example ' HOUBEN-WEYL, Methods of Organic Chemistry, Georg
  • the condensation is advantageously carried out with the addition of a dehydrating agent such as acetic anhydride, a base such as ammonia, ethylamine, piperidine, pyridine or a salt such as ammonia acetate or piperidinium acetate.
  • a dehydrating agent such as acetic anhydride
  • a base such as ammonia, ethylamine, piperidine, pyridine or a salt such as ammonia acetate or piperidinium acetate.
  • an inert solvent such as hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene.
  • the reaction temperature is usually between 0 ° and + 250 ° C, preferably between + 20 ° and +150 ° C. At these temperatures, the reactions are usually complete after 15 minutes to 48 hours.
  • Stilbene derivatives can be prepared, for example, by a Wittig reaction or also by a Wittig-Horner reaction from corresponding aromatic aldehydes and corresponding arylmethylphosphonium salts or phosphonates.
  • a (He ero) aryl halide is reacted with an olefin in the presence of a tertiary arain and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. If2_ (1979) 146).
  • Suitable (he ero) aryl halides are, for example, chlorides, bromides and iodides, in particular bromides.
  • the tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents.
  • Suitable palladium catalysts are, for example, its salts, in particular Pd (II) acetate, together with organic phosphorus (III) compounds such as triarylphosphines.
  • solvents are nitriles such as acetonitrile or hydrocarbons such as benzene or Consider toluene.
  • the (hetero) aryl halides and olefins used as starting materials are widely available commercially or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.
  • the polymers according to the invention also include copolymers consisting of different monomer units a, optionally in a mixture with one or different monomer units b.
  • the monomer ratio a / b depends on various factors, for example the application and the
  • the degree of branching is influenced, among other things, by steric conditions. On the one hand, sterically demanding monomers are less prone to branching, and on the other hand the degree of branching is to a certain extent also dependent on the space available for branching.
  • the nonlinear optical arrangements according to the invention can be manufactured in various ways. For example, they can be prepared by first preparing a polymer according to the invention in an inert solvent, applying it to a substrate surface, for example glass, by spin coating, brushing, printing or dipping, and then aligning it dipolar. The alignment is expediently carried out at a temperature which is in the vicinity of the glass transition temperature of the polymer, preferably by means of an electrical field. The temperature can be both above and below the glass transition temperature.
  • the monomers can also be in bulk, i.e. can be poly erized without solvent, for example on the substrate surface. If the polymerization is carried out in bulk on the substrate surface, then either after the polymerization, as mentioned, can be dipolar-oriented or the polymerization is already polymerized with an applied field, preferably an electric field, a dipolar orientation already occurring.
  • the polymerization on the substrate surface can also be designed in such a way that the monomers are applied to the surface from the gas phase by selecting the test conditions such that the monomers polymerize at the same time.
  • This method is advantageous, for example, in the case of monomers which interact strongly with the surface, for example on account of amphiphilic properties.
  • the monomers predominantly interact selectively with the surface, a first monomer layer oriented overall in the same direction being formed, so that the subsequent polymerization proceeds in such a way that the finished polymer material already has a diplomatic orientation.
  • Suitable for this are, for example, monomers with terminal nitrogen heterocycles, for example pyridine derivatives, in which the ring nitrogen can interact with the substrate surface.
  • other monomers from the gas phase can also be applied and then polymerized, in which case a dipolar orientation induced by an external field may be required.
  • non-linear optical arrangements can also be produced using the LB method.
  • nonlinear optical polymer materials according to the invention are amorphous and are therefore distinguished by their low optical attenuation of ⁇ 1dB cm " .
  • Light-scattering effects such as occur with crystalline or partially crystalline polymers, adversely affect the usability of the materials in nonlinear optics These effects do not occur or only occur to an insignificant extent in the arrangements according to the invention.
  • the polymer materials according to the invention open up a further broad field of application.
  • the polymer materials according to the invention are suitable, for example, for use in optical components. They can thus be used in bulk materials, on the one hand, and in waveguide structures, on the other hand, using the electro-optical effect or for frequency doubling and frequency mixing.
  • the polymer materials according to the invention may themselves function as waveguides.
  • the thickness of the polymer layers depends on the application. When used as a single-mode waveguide, a layer thickness in the micrometer range of approximately 1-10 ⁇ m is advantageous, in particular up to approximately 7 ⁇ m.
  • Nonlinear optically active overlay materials on a waveguide structure usually have layer thicknesses in the nanometer range of approximately 50-500 nm.
  • the polymer materials according to the invention are thus suitable, for example, in components in the field of integrated optics, sensor and communications technology, for frequency doubling of laser light, for the production of directional couplers, switching elements, modulators, parametric amplifiers, waveguide structures, light valves, and others Optical components known to those skilled in the art. Optical components are described, for example, in EP 0218938.
  • a suspension of 135 g (0.44 mol) of 4-acetylamino-3'-cyano-4'-nitrostilbene in a mixture of 260 ml of 37% aqueous hydrochloric acid and 1100 ml of ethanol is boiled for 48 hours. The mixture is allowed to cool and the precipitate is filtered off. This is poured into 200 ml of 35% sodium hydroxide solution, the mixture is then stirred for 4 hours and filtered. The residue is recrystallized from acetone / ethanol. Dark red crystals are obtained.
  • the compound is prepared from the product 2b) as described in Example ld).
  • a 15% by weight solution of the polymer from Example 5 is prepared in the NMP.
  • the solution is filtered (filter with a pore diameter of 2 ⁇ ) to remove dust particles.
  • a glass plate (4 cm x 4 cm, thickness: 1.1 mm) coated with ITO (indium tin oxide) is ultrasonically cleaned in neutral soap solution (Extran, Merck) for 10 minutes, then in double distilled Rinsed water and rinsed with isopropanol.
  • the polymer solution is spun onto this glass plate (1000 rpm), then dried in vacuo at 100 ° C. for 4 hours.
  • the film thickness is approximately 1.3 ⁇ m.
  • a semitransparent gold electrode is deposited on this film.
  • a mixture of 99.5% by weight of N, N-bis (6-hydroxyhexyl) -4-amino-4'-nitrostilbenyl-3'-carboxylic acid and 0.5% by weight of p-toluenesulfonic acid is coated with ITO on one ⁇ th glass plate heated to 250 ° C. The melt is spread to form a uniform, approximately 10 ⁇ m thin film. After 4 h, the mixture is allowed to cool to room temperature. The resulting polymer film is, as described in Example 6, vaporized with gold, poled in an electric field and transversely irradiated with laser light. The laser light is partially frequency-doubled.
  • a mixture of 99.5% by weight of N, N-bis (6-hydroxyhexyl) -4-amino-4'-nitrostilbenyl-3'-carboxylic acid and 0.5% by weight of p-toluenesulfonic acid is coated with ITO between two ⁇ teten glass plates, which are arranged at a distance of 20 microns from each other, heated to 240 ° C at an applied electrical voltage of 100 V. After 1 h, the mixture is allowed to cool to room temperature and the voltage is switched off. Transversely irradiated laser light (example 6) is partially frequency-doubled.
  • Example 3 c A sample of 4- (2- (4-bis (3-chloropropyl) aminophenyl) ethenyl) pyridine (Example 3 c) is, as described in Example 8, polymerized between two ITO electrodes with applied voltage. However, the temperature is

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Matières polymères à base de polymères à chaîne fondamentale, contenant des unités monomères polaires. Les unités monomères polaires contiennent des systèmes π conjugués à substitution de donneurs/accepteurs d'électrons et sont orientées dans le même sens dans les chaînes fondamentales des polymères. Les polymères à chaîne fondamentale sont ramifiés. Ces matières polymères sont particulièrement bien adaptées à des applications dans des éléments optiques en optique non-linéaire.
PCT/EP1990/000546 1989-04-20 1990-04-06 Matieres polymeres ramifiees a orientation dipolaire Ceased WO1990012831A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19893912922 DE3912922A1 (de) 1989-04-20 1989-04-20 Verzweigte, dipolar orientierte polymermaterialien
DEP3912922.5 1989-04-20

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Publication Number Publication Date
WO1990012831A1 true WO1990012831A1 (fr) 1990-11-01

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EP (1) EP0423268A1 (fr)
JP (1) JPH03505473A (fr)
DE (1) DE3912922A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0583608A1 (fr) * 1992-07-13 1994-02-23 Eastman Kodak Company Polyesters cycloalkyl à ramifications multiples et leur préparation
WO1995002581A1 (fr) * 1993-07-12 1995-01-26 Minnesota Mining And Manufacturing Company Composes azoiques optiquement non lineaires contenant un groupe benzimidazole et polymeres derives de ces composes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10934395B2 (en) * 2018-06-15 2021-03-02 Pbi Performance Products, Inc. Polybenzimidazole oligomers with reactive end groups

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172012A2 (fr) * 1984-08-13 1986-02-19 Celanese Corporation Substrats polymères cristal liquide à orientation moléculaire orthogonale
US4579915A (en) * 1985-07-02 1986-04-01 Celanese Corporation Polybenzimidazole polymers exhibiting nonlinear optical effects
US4757130A (en) * 1987-07-01 1988-07-12 Hoechst Celanese Corporaton Condensation polymers with pendant side chains exhibiting nonlinear optical response

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172012A2 (fr) * 1984-08-13 1986-02-19 Celanese Corporation Substrats polymères cristal liquide à orientation moléculaire orthogonale
US4579915A (en) * 1985-07-02 1986-04-01 Celanese Corporation Polybenzimidazole polymers exhibiting nonlinear optical effects
US4757130A (en) * 1987-07-01 1988-07-12 Hoechst Celanese Corporaton Condensation polymers with pendant side chains exhibiting nonlinear optical response

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0583608A1 (fr) * 1992-07-13 1994-02-23 Eastman Kodak Company Polyesters cycloalkyl à ramifications multiples et leur préparation
WO1995002581A1 (fr) * 1993-07-12 1995-01-26 Minnesota Mining And Manufacturing Company Composes azoiques optiquement non lineaires contenant un groupe benzimidazole et polymeres derives de ces composes

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DE3912922A1 (de) 1990-10-25
JPH03505473A (ja) 1991-11-28
EP0423268A1 (fr) 1991-04-24

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