WO1994001480A1 - Polyurethanes non lineaires a activite optique presentant des temperatures elevees de transition vitreuse - Google Patents

Polyurethanes non lineaires a activite optique presentant des temperatures elevees de transition vitreuse Download PDF

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Publication number
WO1994001480A1
WO1994001480A1 PCT/EP1993/001587 EP9301587W WO9401480A1 WO 1994001480 A1 WO1994001480 A1 WO 1994001480A1 EP 9301587 W EP9301587 W EP 9301587W WO 9401480 A1 WO9401480 A1 WO 9401480A1
Authority
WO
WIPO (PCT)
Prior art keywords
optically active
group
linear optically
donor
linear
Prior art date
Application number
PCT/EP1993/001587
Other languages
English (en)
Inventor
Bernardus Henrikus Maria Hams
Franciscus Cornelis Jacobus Maria Van Veggel
Cornelis Petrus Jacobus Maria Van Der Vorst
Original Assignee
Akzo Nobel N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to KR1019950700049A priority Critical patent/KR950702587A/ko
Priority to JP6502871A priority patent/JPH08501811A/ja
Priority to EP93914688A priority patent/EP0650502A1/fr
Priority to CA002139671A priority patent/CA2139671A1/fr
Publication of WO1994001480A1 publication Critical patent/WO1994001480A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3836—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing azo groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/384—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing nitro groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
    • 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
    • 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
    • G02F1/3617—Organic materials containing polymers having the non-linear optical group in a side chain

Definitions

  • the invention relates to a non-linear optically active polyurethane comprising a polymeric main chain and a donor-rr-acceptor sidegroup.
  • Such non-linear optically active polyurethanes are known from EP 0350 112, which discloses non-linear optically active polyurethanes comprising a donor-rr-acceptor group of which the donor group comprises an oxygen atom or nitrogen atom coupled directly to a benzene ring of the rr-acceptor system, with the rr-system being a stilbene group.
  • non ⁇ linear polarisation When polymeric non-linear optically active material is poled, non ⁇ linear polarisation will be effected in it under the influence of an external field of force (such as an electric field of force).
  • Non ⁇ linear electric polarisation may give rise to a number of optically non-linear phenomena, such as frequency doubling and Pockels effect.
  • optically active waveguiding structures such as optical switches, frequency doublers, etc. in the form of a poled film.
  • the present invention has for its object to obviate these drawbacks and provide a non-linear optically active polymer of which the poled film is thermally stable without the polability being negated.
  • the invention consists in that the sidegroup of the non-linear optically active polyurethane comprises a rigid donor group which is also part of the polymeric main chain.
  • the invention also relates to non-linear optically active polyurethanes having a Tg above 170°C.
  • a rigid donor group which may be used in the donor- rr-acceptor sidegroups of a polymer, e.g., in the donor-rr-acceptor sidegroups of polyurethanes.
  • this publication makes no mention of the fact that the use of such rigid donor groups will result in non-linear optically active polymers having high T g s. In fact, this document fails to so much as mention T g s.
  • Suitable rigid donor groups include alicyclic groups containing nitrogen or sulphur. These groups were found to render the bond between the donor-rr-acceptor sidegroup and the main chain so rigid as to give a polyurethane of high Tg without the polability of the polymeric material being negated. Examples of such donor groups are shown in formulae 1-5 below, in which FG represents a functional group. These functional groups may be the same or different.
  • Pyrrolidine groups (according to formula 2) in which the nitrogen atom is coupled directly to the ---acceptor group and dithiafulvene groups (according to formula 1) in particular were found to be highly suitable for obtaining optically non-linear active polyurethanes of good thermal stability and polability.
  • substituted stilbene groups such as nitrostilbene groups, cyanostilbene groups, sulphonate stilbene groups, and sulphonyl stilbene groups
  • substituted azo compounds such as paranitro azobenzene, cyano azobenzene, sulphonyl azobenzene, and sulphonate azobenzene
  • substituted benzylidene aniline compounds such as cyanobenzylidene aniline, nitrobenzylidene aniline, etc.
  • optically non-linear active polyurethanes are obtained from polymerising a diisocyanate with a diol.
  • the donor-rr-acceptor sidegroup may be present in either the diisocyanate or the diol.
  • the invention is also addressed to dihydroxy-functionalised donor-rr- acceptor groups comprising a 3,4-dihydroxy-pyrrolidine group. It was found that these diols, which have not been disclosed before, are easy to prepare, while their polymerisation with diisocyanates gives polyurethanes of outstanding non-linear optically active behaviour. Such diols satisfy formula 6 below:
  • R- is -H, or an alkyl group having 1-3 carbon atoms
  • R3 is an alkyl or aryl group having 1-8 carbon atoms
  • n is an integer from 0 to 4
  • the X groups may be the same or different if n is greater than 1.
  • diisocyanates may be mentioned: isophorone diisocyanate (IPDI), methylene di (p-phenylene isocyanate) (MDI), methylene di (cyclohexylene-4-isocyanate) , toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), paraphenylene diisocyanate (PPDI), and cyclohexylene diisocyanate.
  • IPDI isophorone diisocyanate
  • MDI methylene di (p-phenylene isocyanate)
  • MDI methylene di (cyclohexylene-4-isocyanate)
  • TDI methylene di (cyclohexylene-4-isocyanate)
  • HDI hexamethylene diisocyanate
  • PPDI paraphenylene diisocyanate
  • cyclohexylene diisocyanate cyclohexylene diisocyanate
  • the polyurethanes may be applied to a substrate by means of spincoating.
  • Solvents that are suitable satisfy the following requirements: firstly, of course, the polyurethane must be soluble in the solvent. Further, the solvent should effect proper wetting of the substrate. The polymer solution formed must be filterable and, finally, the solvent should have a boiling point above 80°C to ensure that the solvent does not already evaporate during the spincoating process. Solvents satisfying these requirements for a silicon substrate or glass substrate include cyclopentanone and 2-methyl cyclohexanone. After evaporation of the solvent the thus formed film may be poled, for instance using the so-called DC-induced Pockels effect technique.
  • both an AC and a DC voltage are applied to the sample.
  • the DC field orients the molecules and induces the Pockels effect, while the AC field serves to measure the Pockels coefficient.
  • the strength of the DC field ranges from 10 to 30 V/ ⁇ m.
  • the invention also relates to a non-linear optically active waveguide comprising a non-linear optically active polyurethane according to the invention.
  • Polyurethane 1 was prepared with isophorone diisocyanate (IPDI) according to the general polymerising method disclosed hereinbefore.
  • IPDI isophorone diisocyanate
  • Polyurethane 2 was prepared according to the above-described general polymerising method using isophorone diisocyanate (IPDI). The Tg was measured by DSC and was 200°C.
  • IPDI isophorone diisocyanate
  • Test samples were made of the prepared optically non-linear active polymers for use in Fabry-Perot experiments (r- ⁇ 3) and crossed polariser experiments ( ⁇ -r- ) in transmission.
  • a polyurethane layer provided between two planeparallel , semi- transparent metal electrodes was applied to a glass substrate.
  • the substrate Prior to being metallised in a Balzers evaporation chamber, the substrate was cleaned in situ with a glow discharge.
  • the polyurethane was dissolved in cyclopentanone and filtered through a miHipore ® filter having a pore size of 0,45 ⁇ m.
  • the films were prepared by spincoating. After the spincoating process the samples were placed on a hot stage and heated slightly above Tg for 0.5-3 hours.
  • the polyurethane film 1 and 2 were poled using the DC-induced Pockels effect technique as described hereinbefore at a temperature above the polyurethane's T g (180°C and 200°C, respectively) for 15 minutes.
  • the freezing in efficiency 1 7 i.e., the ratio of the Pockels coefficient (ri3) for a switched off DC-field after freezing in at room temperature to the Pockels coefficient for the switched on DC-field, r 13 field off/ r 13 field on
  • TABLE 1 also lists the Tg (measured by DSC) and the Pockels coefficients ⁇ 33
  • the relaxation measurements were carried out at various temperatures.
  • the temperatures employed for polyurethane 1 and 2 were in the range of 100°to 175°C, for polyurethane 3* they were in the range of 100° to 135°C. These values were plotted in an Arrhenius plot and from them the values of the half-life, i.e., the time which signifies the loss of 50% of the Pockels coefficient, could be calculated.
  • the half-life (t ) is indicative of the film's stability. The results are compiled in TABLE 1.
  • the data shows that fi lms prepared from the opti cal ly non-l i near active polyurethanes accordi ng to the i nvention have a higher Tg than the already known optically non-linear active polyurethanes, and can be poled.
  • the thermal stability of poled films containing polyurethanes according to the invention was found to be much higher at elevated temperatures such as 140°-160°C than that of poled films of already known optically non-linear active polyurethanes. This means that the optically non-linear active polyurethanes according to the invention are highly resistant to momentary heating such as occurs in soldering.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Polyuréthane non linéaire à activité optique comportant une chaîne principale polymère et un groupe latéral donneur-π-accepteur. Ce groupe latéral comporte un groupe donneur rigide également compris dans la chaîne principale polymère. L'incorporation de groupes donneurs rigides dans le polyuréthane non linéaire à activité optique permet d'obtenir une température élevée de transition vitreuse (Tg supérieure à 170 °C), et d'augmenter ainsi la stabilité thermique. On a également prévu des polyuréthanes non linéaires à activité optique dont la Tg est supérieure à 170 °C, ainsi que des guides d'ondes non linéaires à activité optique comportant des polyuréthanes non linéaires à activité optique du type précité. Les groupes donneurs rigides appropriés sont notamment les groupes alicycliques contenant du soufre ou de l'azote. Plus spécialement, il s'avère que les groupes dihydroxy-pyrrolidine dans lesquels l'atome d'azote est couplé directement au groupe π-accepteur, ainsi que les groupes dithiafulvène, sont très utiles dans la préparation de polyuréthanes non linéaires à activité optique présentant une bonne stabilité thermique et une bonne polarisabilité.
PCT/EP1993/001587 1992-07-06 1993-06-21 Polyurethanes non lineaires a activite optique presentant des temperatures elevees de transition vitreuse WO1994001480A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1019950700049A KR950702587A (ko) 1992-07-06 1993-06-21 고 유리 전이 온도를 가진 비 선형 광학 활성 폴리우레탄(non-linear potically active polyurethanes having high glass transition temperatures)
JP6502871A JPH08501811A (ja) 1992-07-06 1993-06-21 高いガラス転移温度を有する非線形光学活性ポリウレタン
EP93914688A EP0650502A1 (fr) 1992-07-06 1993-06-21 Polyurethanes non lineaires a activite optique presentant des temperatures elevees de transition vitreuse
CA002139671A CA2139671A1 (fr) 1992-07-06 1993-06-21 Polyurethanes non linaires optiquement actifs a temperatures elevees de transition vitreuse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9201202 1992-07-06
NL9201202 1992-07-06

Publications (1)

Publication Number Publication Date
WO1994001480A1 true WO1994001480A1 (fr) 1994-01-20

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PCT/EP1993/001587 WO1994001480A1 (fr) 1992-07-06 1993-06-21 Polyurethanes non lineaires a activite optique presentant des temperatures elevees de transition vitreuse

Country Status (6)

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EP (1) EP0650502A1 (fr)
JP (1) JPH08501811A (fr)
KR (1) KR950702587A (fr)
CN (1) CN1083494A (fr)
CA (1) CA2139671A1 (fr)
WO (1) WO1994001480A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996028757A1 (fr) * 1995-03-13 1996-09-19 Akzo Nobel N.V. Polycarbonates optiques non lineaires
US5588083A (en) * 1993-09-29 1996-12-24 Akzo Nobel N.V. Non-linear optically active polycarbonate
EP0780722A1 (fr) * 1995-12-22 1997-06-25 Akzo Nobel N.V. Dispositif électro-optique stable dans la gamme de longueurs d'ondes entre 600 et 1600 nanomètres
US5688896A (en) * 1994-09-26 1997-11-18 Akzo Nobel N.V. Non-linear optically active polycarbonate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358476A2 (fr) * 1988-09-08 1990-03-14 Akzo Nobel N.V. Systèmes optiques intégrés
EP0401063A1 (fr) * 1989-05-03 1990-12-05 Flamel Technologies Polymères actifs en optique non linéaire
US4985528A (en) * 1988-09-16 1991-01-15 Rhone-Poulenc Chimie Novel nonlinearly optically active polyurethanes
EP0445864A1 (fr) * 1990-03-06 1991-09-11 Akzo Nobel N.V. Système NLO thermodurcissable et les composantes optiques intégrées à partir de celui-ci
EP0477666A1 (fr) * 1990-09-24 1992-04-01 Siemens Aktiengesellschaft Epoxy-résines réticulées à propriétés optiques non-linéaires

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358476A2 (fr) * 1988-09-08 1990-03-14 Akzo Nobel N.V. Systèmes optiques intégrés
US4985528A (en) * 1988-09-16 1991-01-15 Rhone-Poulenc Chimie Novel nonlinearly optically active polyurethanes
EP0401063A1 (fr) * 1989-05-03 1990-12-05 Flamel Technologies Polymères actifs en optique non linéaire
EP0445864A1 (fr) * 1990-03-06 1991-09-11 Akzo Nobel N.V. Système NLO thermodurcissable et les composantes optiques intégrées à partir de celui-ci
EP0477666A1 (fr) * 1990-09-24 1992-04-01 Siemens Aktiengesellschaft Epoxy-résines réticulées à propriétés optiques non-linéaires

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5588083A (en) * 1993-09-29 1996-12-24 Akzo Nobel N.V. Non-linear optically active polycarbonate
US5688896A (en) * 1994-09-26 1997-11-18 Akzo Nobel N.V. Non-linear optically active polycarbonate
WO1996028757A1 (fr) * 1995-03-13 1996-09-19 Akzo Nobel N.V. Polycarbonates optiques non lineaires
US5872882A (en) * 1995-03-13 1999-02-16 Akzo Nobel Nv Non-linear optical polycarbonates
EP0780722A1 (fr) * 1995-12-22 1997-06-25 Akzo Nobel N.V. Dispositif électro-optique stable dans la gamme de longueurs d'ondes entre 600 et 1600 nanomètres
WO1997023807A1 (fr) * 1995-12-22 1997-07-03 Akzo Nobel N.V. Dispositif electro-optique ou opto-optique, stable dans la gamme de longueur d'ondes de 600-1600 nanometres
US5776375A (en) * 1995-12-22 1998-07-07 Akzo Nobel N.V. Electro-optical device stable in the 600-1600 nanometer wavelength range

Also Published As

Publication number Publication date
EP0650502A1 (fr) 1995-05-03
CA2139671A1 (fr) 1994-01-20
KR950702587A (ko) 1995-07-29
CN1083494A (zh) 1994-03-09
JPH08501811A (ja) 1996-02-27

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