CA2139671A1 - Non-linear optiically active polyurethanes having high glass transition temperatures - Google Patents
Non-linear optiically active polyurethanes having high glass transition temperaturesInfo
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- CA2139671A1 CA2139671A1 CA002139671A CA2139671A CA2139671A1 CA 2139671 A1 CA2139671 A1 CA 2139671A1 CA 002139671 A CA002139671 A CA 002139671A CA 2139671 A CA2139671 A CA 2139671A CA 2139671 A1 CA2139671 A1 CA 2139671A1
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- Prior art keywords
- optically active
- group
- donor
- linear optically
- linear
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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
- 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
- C08G18/67—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
- 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
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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
The invention relates to a non-linear optically active polyurethane comprising a polymeric main chain and a donor-.pi.-acceptor sidegroup, with the sidegroup comprising a rigid donor group which is also part of the polymeric main chain. By incorporating rigid donor groups into the non-linear optically active polyurethane a high glass transition temperature (Tg above 170 ·C) is obtained, and hence increased thermal stability. The invention further relates to non-linear optically active polyurethanes having a Tg above 170 ·C, and to non-linear optically active waveguides comprising non-linear optically active polyurethanes according to the invention. Suitable rigid donor groups include nitrogen- or sulphur-containing alicyclic groups. In particular, dihydroxy pyrrolidine groups in which the nitrogen atom is directly coupled to the .pi.-acceptor group and dithiafulvene groups were found to be highly suitable for obtaining non-linear optically active polyurethanes of good thermal stability and polarizability.
Description
WO 94~01480 21~ 9 6 71 PCl~EPg3/01587 NON-LINEAR OPTICALLY ACTIVE POLYURETHANES HAVING HIGH GLASS TRANSITION
TEMPERATURES
The invention relates to a non-linear optically active polyurethane comprising a polymeric main chain and a donor-~-acceptor sidegroup.
Such non-linear optically active polyurethanes are known from EP O 350 112, which discloses non-linear optically active polyurethanes comprising a donor-~-acceptor group of which the donor group comprises an oxygen atom or nitrogen atom coupled di~ectly to a benzene ring of the ~-acceptor system, with the ~-system being a stilbene group.
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.
By utilising these phenomena it is possible to employ this material in optically active waveguiding structures such as optical switches, frequency daublers, etc. in the form of a poled film.
, - While the stability of poled films made of the present non-linear optically active polymers is excellent at room temperature, it leaves something to be desired at elevated temperature: relaxation results in lower values of the Pockels coefficients (r33 an~ r13, in this description it is assumed that r33 = 3 x r13). The Pockels coefficient ' (r33) is indicative of the non-linear optical behaviour of the film.
The poor thermal stability of poled films of known non-linear optically active polymers gives rise to problems especially when the polymer is briefly heated to 200-300C during soldering. Neither are ~~ the present non-linear optically active polymers suitable for constant use at elevated operating temperatures in the range of 60 to 120C.
To enhance thermal stability efforts have been made, int. al., to WO 94/01480 PCI'/EP93/01587 21391~71 render non-linear optically active polyacrylates less flexible by omitting the conventional spacers between the main chain and the donor-~-acceptor sidegroup. However, it was found that such polyacrylates could not be poled.
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. To this end 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.
- Polyurethanes do not require spacers. When rigid donor groups are employed, these are in effect incorporated into the main chain, thus giving a rigid bond between the donor-~-acceptor sidechain and the main chain. For further elucidation a schematic depiction is provided in Figure 1.
: ~ ~ 20 ` . :
~, - . - ~
-- - _ Figure 1 WO 94~01480 PCr/EP93/01587 wherein D represents a donor group, n stands for a ~-system, A is an acceptor group, and H is the main chain of the polyurethane.
The result of this is a higher glass transition temperature (Tg above 170C) and hence a higher thermal stability also. It was found that such polyurethanes could be poled. Since polable non-linear optically active polyurethanes of such a high Tg were hitherto unknown, the invention also relates to non-linear optically active polyurethanes having a Tg above 170C. Among the many donor groups enumerated in EP-A2-0 358 476 is a rigid donor group which may be used in the donor-~-acceptor sldegroups of a polymer, e.g., in the donor-~-acceptor sidegroups of polyurethanes. However, 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 Tgs. In fact, this document fails to so much as mention Tgs.
Suitable rigid donor groups include alicyclic groups containing nitrogen or sulphur. These groups were found to render the bond between the donor-~-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, ln which FG represents a functional group. These functional groups may be the same or different.
_ .
, FG
j ~ G iO~FG
formula 1formula 2 formula 3 -G ~c FC .c 5 /~
fonmula 4 : formula 5 Pyrrolidine groups (according to formula 2) in which the nitrogen atom is coupled direc~ly to the ~-acceptor group and dithiafulvene groups (according to formula 1) in particular were found to be highly suitable for obtaining optically non-linear ac~ive polyurethanes of good thermal stability and polability.
It is possi~le in principle for any n-acceptor group to be coupled to the donor groups according to the invention. As examples may be mentioned: substituted stilbene groups, such as nitrostilbene groups, -cyanostilbene groups, sulphonate stilbene groups, and sùlphonyl stilbene groups, substituted azo compounds, such ~as paranitro azobenzene, cyano azobenzene, sulphonyl azobenzene~ and sulphonate azobenzene, substituted benzylidene aniline compound~, -such as cyanobenzylidene anillne, nitrobenzylidene aniline, etc.
:i In general, optically non-linear active polyurethanes are obtained from polymerising a diisocyanate with a diol. The ~donor-~-acceptor sidegroup may be present in either the diisocyanate or the diol. The functional groups in the fonmulae 1-5 will the~`stand for -N=C=0 and -(CH2)n-OH (n=0 or 1), respectively. Since -hydroxy-functionalised donor-~-acceptorgroups are easy to prepare, their employment in combination with diisocyanates which do not -contain donor-~-acceptor groups is preferred.
WO 94/01480 PCI'/EP93/01587 The invention is also addressed to dihydroxy-functionalised donor-~-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 fonmula 6 below:
OH OH
~
- Rl formula 6 (X)n R l y wherein X is -CR~=DR~-, -N=N-, -CR~=N- or -N=CR~-, Y is -~N, -N02, CR2=C(CN)2, -CF3, -CCN=C(CN)2 or R~ is -halogen, -R2, -OR2, -COR2, COOR2, -CN or -CF3, R2 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 O to 4, and the X groups may be the same or different if n is greater than 1.
As suitable 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), -W o 94/01480 213 9 6 71 PCT/EP93/01587 and cyclohexylene diisocyanate. Alternatively, it is possible to employ diisocyanate mixtures in the polyurethane. It is preferred to utilise rigid diisocyanates, such as IPDI9 MDI, and TDI, since these will give maximum Tg.
After being dissolved in an appropriate solvent 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 80C 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 t~he thus formed film may be poled, for instance using the so-called DC-induced Pockels effect technique. In this process 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.
The invention will be further illustrated with reference to several unlimitative examples, which are submitted solely for a better understanding of the invention.
.~ .
_ 30 WO 94/01480 PCI/EP93/0158i EXAMPLES
General polymerising method 10 mmoles of diisocyanate (or diisocyanate mixture) were fed to 10 mmoles of diol with donor-~-acceptor group in 20 ml of dry dimethyl formamide (DMF). The mixture was stirred under nitrogen at room temperature for 30 minutes. The temperature was then slowly increased to 90C, and on conclusion of the reaction the reaction mixture was diluted with 10 ml of DMF and filtered. The clear solution was precipitated in 300 ml of ethanol. The precipitated polymer was filtered off, washed twice with 100 ml of methanol being employed each time, and dried.
example 1: polyurethane of dimethylol dithiafulvene nitrostilbene and (IPDI) (polyurethane 1) synthesis of dimethylol dithiafulvene nitrostilbene (diol 1): cf.
diagram 1 Step 1:
To a solution of 7,6 9 (100 mmoles) of CS2, 20,8 9 (100 mmoles) of ~ompQund -~~,~and 50 ml of Et20 were added slowly and dropwise at 0C
-20,2 9- of~ (n-Bu)3P. After cooling to -25C 14,2 g (100 mmoles) of dimethyl acetylene dicarboxylate (DMAD) were added dropwise. Next, the whole was stirred at 0C for one hour. After the addition of CH2Cl2 the reaction product was riltered through SiO2, washed with CH2Cl2, and concentrated. The reaction product was purified by Flash column --c~r~matography (SiO2: ethyl acetate/n-hexane (1/9)). Compound 2 was ~ obtained in a 57 mole% yield.
WO 94/0148() PCr/EP93/01587 21~9671 Step 2:
The pH of a solution of 25 9 (61,0 mmoles) of compound 2 in 450 ml of THF and 250 ml of water containing p-TosOH was set at 2, after which the solution was stirred for 16 hours. After 1 l of water had been added the whole was extracted using ethyl acetate. The organic layer was washed with NaHC03 solution and brine, dried on MgS04, filtered, and concentrated. Recrystallisation fr~m MeOH gave compound 3 in a 75 mole% yield.
Step 3:
To a solution of 6,72 9 (20 mmoles) of compound 3 in 7,24 9 (40 mmoles) of nitrophenyl acetic acid and 60 ml of DMF were added slowly and dropwise 3,4 9 (40 mmoles) of piperidine. After being stirred for 18 hours the reaction mixture was poured in water. The solid was fil~ered off, washed, and dried. Recrystallisation from CH3CN gave compound 4 in a 86 mole% yield.
Step 4:
.
To a mixture of l,OO 9 (2,2 mmoles) of compound 4, 1,22 9 (11,0 mmoles) of CaCl2, 30 ml of THF, and 20 ml of EtOH were slowly added 0,42 9 (11,0 mmoles) of-Na3H4-. ~t ~the end of the reaction H20 was added, and the whole was ext-racted using ethyl acetate. The organic layer was washed with water and brine, dried on MgS04, filtered, and concentrated. Recrystallisation from CH3CN gave diol 1 in a 90 mole%
yield.
_ 213~671 Step 5:
A solution of 5 g (12,5 mmoles) of compound 5, la ml of THF, and 10 ml of AC20 was stirred at 100C for 2 hours . After cooling ethyl acetate was added, and the whole was washed with NH4CL solution and brine, dried on M~S04, filtered, and concentrated. Recrystallisation from CH3CN gave compound 6 in a 40 mole% yield.
Step 6:
A solution of 15 9 (31,1 mmoles) of compound 6, 300 ml of 10%-NaOH
sol uti on, and 1000 ml THF was kept at refluxing temperature for one hour. A~ter cooling the layers were separated and the organic layer was washed with brine, dried on MgS04, filtered, and concentrated.
After agitation with 400 ml of MeOH and filtering off diol 1 was obtai ned i n a 83 mole% yield.
Polyurethane 1 was prepared with isophorone diisocyanate (IPDI) according to the general polymerising method disclosed hereinbefore.
For the Tg reference is made to TABLE 1.
example 2: polyurethane of dihydroxypyrrolidine ~~nitrostilbene and ~IPDI) (polyurethane 2) synthesis of dihydroxypyrrolidine nitr~stilbene (d1ol- 2):-For the preparation of compound 1 reference is made to J. Am. Chem.
Soc. 76 (1954), 3584.
Step 1: -11,4 g (63,7 mmoles) of compound 1, 16,3 g t~5S,2 mm~les) of aceticanhydride, 60 ml of THF and 2 ml of triethyl amine were kept at refluxing temperature for 18 hours. After~concentration by evaporation WO 94/01480 PCl'/EP93/01587 21396~1 - --200 ml of ethyl acetate were added, and the mixture was neutralised with a saturated NaHC03 501 ution. The layers were separated, and the organic layer was dried on MgS04. After filtration and concentration, recrystallisation from THF gave compound 2 in a 95 mole% yield.
Step 2:
~ ' 8,83 9 (57,7 mmoles) of POCl3 were added dropwise to 20 ml of DMF at a temperature below 10C. Next, the whole was stirred at room temperature for one hour. Subsequently, a solution of 13,8 g (52,5 mmoles) of compound 2 and 12 ml of DMF were added dropwise, and the whole was stirred at 70C for 2 hours. The reaction mixture, after being cooled down, was poured in ice/water and~ neutralised with 18,5 9 (225 mmoles) of sodium acetate. Next, the whole was extracted with 15~ C~2Cl2~, and the organic layer was washed with H20 and brine, dried on Mg~S04, filtered, and concentrated. The solid was recrystallised from MeOH and compound 3 was obtained in an 88 mole% yield.
, S~ep 3:
To 2,12 3 (52,8 mmo~es) of NaH (60% in oil) a solution of 13,0 9 (44,7 ~
~-~ mmoles~ of compound 3, 12,0 9 (44,0 mmoles) of compound 4, and 150 ml of DMF~was added slowly and dropwise, with stirring. The mixture was stirred for 18 hours and the poured in 1,5 1 of water. After bein~ -sttrred for one hour the mixture was filtered and washed with H20. The solid was dissolved in ethyl acetate, washed with a saturated NaHCO~ -solution and brine, dried on MgS04, filtered, and concentrated. After purification by column chromatography (SiO2/CH2Cl2) compound 5 was: ~ ~
obtained in an 80 mole% yield. -- -_ _ _ ' , WO 94~01480 PCa/~P93/~1~87 Step 4:
A solution of 14,0 9 (36,3 mmoles) of compound 5 in 200 ml of THF was added dropwise to a suspension of 4,32 9 (80 mmoles) of NaOMe and 50 ml of MeOH. After one hour of stirring 100 ml of MeOH were added and the reaction mixture was poured in H20 The solid was dissolved in ethyl acetateS washed with saturated NaHC03 solution and brine, dried on MgSOq, filtered, and concentrated. After purification by Flash chromatography (SiO2: CH2Cl2tn-hexane (95/5)) diol 2 was obtained in a 90 mole% yield.
Polyurethane 2 was prepared according to the above-described general polymerising method using isophorone di-isocyanate (IPDI). The Tg was measured by DSC and was 200C.
comparison example: polyurethane of 4-di-(2-hydroxyethyl)amino-4'-nitrostilbene and (IPDI) .
For the preparation of 4-di-(2-hydroxyethyl)amino-4'-nitrostilbene reference is made to EP-A1-0 350 112. Po1yurethane 3* was prepared by means of the above-described conventional polymerising method using this diol and isophorone diisocyanate.
Test samples were made of the prepared optically non-linear active polymers for use in Fabry-Perot experiments (r13) and crossed polariser experiments (r33-r13) in transmission. To this end a polyurethane layer provided between two planeparallel, semi-transparent metal electrodes was applied to a glass 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 millipore0 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.
WO 94tO1480 PCrtEP93/01587 ~139~71 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 Tg (180C and 200C, respectively) for 15 minutes~ The freezing in efficiency ~ (i.e., the ratio of the Pockels coefficient (r13) for a switched off DC-field after freezing in at room temperature to the Pockels coefficient for the switched on DC-field, r13 field off/r13 field on) is shown in TABLE 1, which also lists the Tg (measured by DSC~ and the Pockels coefficients (r33), it being assumed that r33 =~ 3 x r13. It proved possible to pole the film of polyurethane 3* at 140C in one minute.
The relaxation measurements were carried out at various temperatures.
The temperatures employed for polyurethane 1 and 2 were in the range of 100to 175C, for polyurethane 3* they were in the range of 100 to 135C. These values were plotted in an Arrhenius plot and from them the values of the half-life, i.e., the ttme 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 2a in TABLE 1.
TABLE I
~, _ . . ---25-polyurethan~ Tg r33 ~ t~
(oo) (pm7V) (%) (ho~r) at:
. _ 1 175 1,3 40 S,88 1,21 0,73 2 200 1,2 45 20,6 4,5 2,78 3~ ~--3* 140 2,2 60 0,0108 0,00027 0,00008C
_ The data shows that films prepared from the optically non-linear active polyurethanes according to the invention have a higher Tg than WO 94/01480 PCl'/EP93/0158i the already known optically non-linear active polyurethanes, and can be poled. In addition, the thermal stability of poled films containing polyurethanes according to the invention was found to be much higher at elevated temperatures such as 140-160C 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.
`- _ WO 94/01480 PCI'/EP93~01587 Dia~am_ 1 CHO
COOMe ¦1 + CS2+ ~)step 1 COOMe C~(OEt) 2 Ct:)OMe COOMe COOMe S ~ COOMe ~J ~COOMe ~COOMe [~ step 2 ~ [~ stel~ 3 CH(OEt)2 CXO
2 ~ ~ 4 CH20H -CH20Ac-- CH20H
~ CH20Ac ~ CH20 ~; _step 5 ~ ~ step 6 ~
N2 5 N2 6 ~2 5 SVBSTJTUTE SHEET
WO 94/01480 2 1 3 9 6 7 1 PCI`/EP93/01587 Diaqram 2 HO ~SOH AcO ~OAc AcO ~OAc steP 1 ~ N steP 2 ~ N
AcO ~OAc HO OH
step 3 ~ ~3 step 4 ~,PO(OEt) 4 NO2 ~ 6 :
SUBSTITUTE SHEEl-
TEMPERATURES
The invention relates to a non-linear optically active polyurethane comprising a polymeric main chain and a donor-~-acceptor sidegroup.
Such non-linear optically active polyurethanes are known from EP O 350 112, which discloses non-linear optically active polyurethanes comprising a donor-~-acceptor group of which the donor group comprises an oxygen atom or nitrogen atom coupled di~ectly to a benzene ring of the ~-acceptor system, with the ~-system being a stilbene group.
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.
By utilising these phenomena it is possible to employ this material in optically active waveguiding structures such as optical switches, frequency daublers, etc. in the form of a poled film.
, - While the stability of poled films made of the present non-linear optically active polymers is excellent at room temperature, it leaves something to be desired at elevated temperature: relaxation results in lower values of the Pockels coefficients (r33 an~ r13, in this description it is assumed that r33 = 3 x r13). The Pockels coefficient ' (r33) is indicative of the non-linear optical behaviour of the film.
The poor thermal stability of poled films of known non-linear optically active polymers gives rise to problems especially when the polymer is briefly heated to 200-300C during soldering. Neither are ~~ the present non-linear optically active polymers suitable for constant use at elevated operating temperatures in the range of 60 to 120C.
To enhance thermal stability efforts have been made, int. al., to WO 94/01480 PCI'/EP93/01587 21391~71 render non-linear optically active polyacrylates less flexible by omitting the conventional spacers between the main chain and the donor-~-acceptor sidegroup. However, it was found that such polyacrylates could not be poled.
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. To this end 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.
- Polyurethanes do not require spacers. When rigid donor groups are employed, these are in effect incorporated into the main chain, thus giving a rigid bond between the donor-~-acceptor sidechain and the main chain. For further elucidation a schematic depiction is provided in Figure 1.
: ~ ~ 20 ` . :
~, - . - ~
-- - _ Figure 1 WO 94~01480 PCr/EP93/01587 wherein D represents a donor group, n stands for a ~-system, A is an acceptor group, and H is the main chain of the polyurethane.
The result of this is a higher glass transition temperature (Tg above 170C) and hence a higher thermal stability also. It was found that such polyurethanes could be poled. Since polable non-linear optically active polyurethanes of such a high Tg were hitherto unknown, the invention also relates to non-linear optically active polyurethanes having a Tg above 170C. Among the many donor groups enumerated in EP-A2-0 358 476 is a rigid donor group which may be used in the donor-~-acceptor sldegroups of a polymer, e.g., in the donor-~-acceptor sidegroups of polyurethanes. However, 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 Tgs. In fact, this document fails to so much as mention Tgs.
Suitable rigid donor groups include alicyclic groups containing nitrogen or sulphur. These groups were found to render the bond between the donor-~-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, ln which FG represents a functional group. These functional groups may be the same or different.
_ .
, FG
j ~ G iO~FG
formula 1formula 2 formula 3 -G ~c FC .c 5 /~
fonmula 4 : formula 5 Pyrrolidine groups (according to formula 2) in which the nitrogen atom is coupled direc~ly to the ~-acceptor group and dithiafulvene groups (according to formula 1) in particular were found to be highly suitable for obtaining optically non-linear ac~ive polyurethanes of good thermal stability and polability.
It is possi~le in principle for any n-acceptor group to be coupled to the donor groups according to the invention. As examples may be mentioned: substituted stilbene groups, such as nitrostilbene groups, -cyanostilbene groups, sulphonate stilbene groups, and sùlphonyl stilbene groups, substituted azo compounds, such ~as paranitro azobenzene, cyano azobenzene, sulphonyl azobenzene~ and sulphonate azobenzene, substituted benzylidene aniline compound~, -such as cyanobenzylidene anillne, nitrobenzylidene aniline, etc.
:i In general, optically non-linear active polyurethanes are obtained from polymerising a diisocyanate with a diol. The ~donor-~-acceptor sidegroup may be present in either the diisocyanate or the diol. The functional groups in the fonmulae 1-5 will the~`stand for -N=C=0 and -(CH2)n-OH (n=0 or 1), respectively. Since -hydroxy-functionalised donor-~-acceptorgroups are easy to prepare, their employment in combination with diisocyanates which do not -contain donor-~-acceptor groups is preferred.
WO 94/01480 PCI'/EP93/01587 The invention is also addressed to dihydroxy-functionalised donor-~-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 fonmula 6 below:
OH OH
~
- Rl formula 6 (X)n R l y wherein X is -CR~=DR~-, -N=N-, -CR~=N- or -N=CR~-, Y is -~N, -N02, CR2=C(CN)2, -CF3, -CCN=C(CN)2 or R~ is -halogen, -R2, -OR2, -COR2, COOR2, -CN or -CF3, R2 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 O to 4, and the X groups may be the same or different if n is greater than 1.
As suitable 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), -W o 94/01480 213 9 6 71 PCT/EP93/01587 and cyclohexylene diisocyanate. Alternatively, it is possible to employ diisocyanate mixtures in the polyurethane. It is preferred to utilise rigid diisocyanates, such as IPDI9 MDI, and TDI, since these will give maximum Tg.
After being dissolved in an appropriate solvent 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 80C 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 t~he thus formed film may be poled, for instance using the so-called DC-induced Pockels effect technique. In this process 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.
The invention will be further illustrated with reference to several unlimitative examples, which are submitted solely for a better understanding of the invention.
.~ .
_ 30 WO 94/01480 PCI/EP93/0158i EXAMPLES
General polymerising method 10 mmoles of diisocyanate (or diisocyanate mixture) were fed to 10 mmoles of diol with donor-~-acceptor group in 20 ml of dry dimethyl formamide (DMF). The mixture was stirred under nitrogen at room temperature for 30 minutes. The temperature was then slowly increased to 90C, and on conclusion of the reaction the reaction mixture was diluted with 10 ml of DMF and filtered. The clear solution was precipitated in 300 ml of ethanol. The precipitated polymer was filtered off, washed twice with 100 ml of methanol being employed each time, and dried.
example 1: polyurethane of dimethylol dithiafulvene nitrostilbene and (IPDI) (polyurethane 1) synthesis of dimethylol dithiafulvene nitrostilbene (diol 1): cf.
diagram 1 Step 1:
To a solution of 7,6 9 (100 mmoles) of CS2, 20,8 9 (100 mmoles) of ~ompQund -~~,~and 50 ml of Et20 were added slowly and dropwise at 0C
-20,2 9- of~ (n-Bu)3P. After cooling to -25C 14,2 g (100 mmoles) of dimethyl acetylene dicarboxylate (DMAD) were added dropwise. Next, the whole was stirred at 0C for one hour. After the addition of CH2Cl2 the reaction product was riltered through SiO2, washed with CH2Cl2, and concentrated. The reaction product was purified by Flash column --c~r~matography (SiO2: ethyl acetate/n-hexane (1/9)). Compound 2 was ~ obtained in a 57 mole% yield.
WO 94/0148() PCr/EP93/01587 21~9671 Step 2:
The pH of a solution of 25 9 (61,0 mmoles) of compound 2 in 450 ml of THF and 250 ml of water containing p-TosOH was set at 2, after which the solution was stirred for 16 hours. After 1 l of water had been added the whole was extracted using ethyl acetate. The organic layer was washed with NaHC03 solution and brine, dried on MgS04, filtered, and concentrated. Recrystallisation fr~m MeOH gave compound 3 in a 75 mole% yield.
Step 3:
To a solution of 6,72 9 (20 mmoles) of compound 3 in 7,24 9 (40 mmoles) of nitrophenyl acetic acid and 60 ml of DMF were added slowly and dropwise 3,4 9 (40 mmoles) of piperidine. After being stirred for 18 hours the reaction mixture was poured in water. The solid was fil~ered off, washed, and dried. Recrystallisation from CH3CN gave compound 4 in a 86 mole% yield.
Step 4:
.
To a mixture of l,OO 9 (2,2 mmoles) of compound 4, 1,22 9 (11,0 mmoles) of CaCl2, 30 ml of THF, and 20 ml of EtOH were slowly added 0,42 9 (11,0 mmoles) of-Na3H4-. ~t ~the end of the reaction H20 was added, and the whole was ext-racted using ethyl acetate. The organic layer was washed with water and brine, dried on MgS04, filtered, and concentrated. Recrystallisation from CH3CN gave diol 1 in a 90 mole%
yield.
_ 213~671 Step 5:
A solution of 5 g (12,5 mmoles) of compound 5, la ml of THF, and 10 ml of AC20 was stirred at 100C for 2 hours . After cooling ethyl acetate was added, and the whole was washed with NH4CL solution and brine, dried on M~S04, filtered, and concentrated. Recrystallisation from CH3CN gave compound 6 in a 40 mole% yield.
Step 6:
A solution of 15 9 (31,1 mmoles) of compound 6, 300 ml of 10%-NaOH
sol uti on, and 1000 ml THF was kept at refluxing temperature for one hour. A~ter cooling the layers were separated and the organic layer was washed with brine, dried on MgS04, filtered, and concentrated.
After agitation with 400 ml of MeOH and filtering off diol 1 was obtai ned i n a 83 mole% yield.
Polyurethane 1 was prepared with isophorone diisocyanate (IPDI) according to the general polymerising method disclosed hereinbefore.
For the Tg reference is made to TABLE 1.
example 2: polyurethane of dihydroxypyrrolidine ~~nitrostilbene and ~IPDI) (polyurethane 2) synthesis of dihydroxypyrrolidine nitr~stilbene (d1ol- 2):-For the preparation of compound 1 reference is made to J. Am. Chem.
Soc. 76 (1954), 3584.
Step 1: -11,4 g (63,7 mmoles) of compound 1, 16,3 g t~5S,2 mm~les) of aceticanhydride, 60 ml of THF and 2 ml of triethyl amine were kept at refluxing temperature for 18 hours. After~concentration by evaporation WO 94/01480 PCl'/EP93/01587 21396~1 - --200 ml of ethyl acetate were added, and the mixture was neutralised with a saturated NaHC03 501 ution. The layers were separated, and the organic layer was dried on MgS04. After filtration and concentration, recrystallisation from THF gave compound 2 in a 95 mole% yield.
Step 2:
~ ' 8,83 9 (57,7 mmoles) of POCl3 were added dropwise to 20 ml of DMF at a temperature below 10C. Next, the whole was stirred at room temperature for one hour. Subsequently, a solution of 13,8 g (52,5 mmoles) of compound 2 and 12 ml of DMF were added dropwise, and the whole was stirred at 70C for 2 hours. The reaction mixture, after being cooled down, was poured in ice/water and~ neutralised with 18,5 9 (225 mmoles) of sodium acetate. Next, the whole was extracted with 15~ C~2Cl2~, and the organic layer was washed with H20 and brine, dried on Mg~S04, filtered, and concentrated. The solid was recrystallised from MeOH and compound 3 was obtained in an 88 mole% yield.
, S~ep 3:
To 2,12 3 (52,8 mmo~es) of NaH (60% in oil) a solution of 13,0 9 (44,7 ~
~-~ mmoles~ of compound 3, 12,0 9 (44,0 mmoles) of compound 4, and 150 ml of DMF~was added slowly and dropwise, with stirring. The mixture was stirred for 18 hours and the poured in 1,5 1 of water. After bein~ -sttrred for one hour the mixture was filtered and washed with H20. The solid was dissolved in ethyl acetate, washed with a saturated NaHCO~ -solution and brine, dried on MgS04, filtered, and concentrated. After purification by column chromatography (SiO2/CH2Cl2) compound 5 was: ~ ~
obtained in an 80 mole% yield. -- -_ _ _ ' , WO 94~01480 PCa/~P93/~1~87 Step 4:
A solution of 14,0 9 (36,3 mmoles) of compound 5 in 200 ml of THF was added dropwise to a suspension of 4,32 9 (80 mmoles) of NaOMe and 50 ml of MeOH. After one hour of stirring 100 ml of MeOH were added and the reaction mixture was poured in H20 The solid was dissolved in ethyl acetateS washed with saturated NaHC03 solution and brine, dried on MgSOq, filtered, and concentrated. After purification by Flash chromatography (SiO2: CH2Cl2tn-hexane (95/5)) diol 2 was obtained in a 90 mole% yield.
Polyurethane 2 was prepared according to the above-described general polymerising method using isophorone di-isocyanate (IPDI). The Tg was measured by DSC and was 200C.
comparison example: polyurethane of 4-di-(2-hydroxyethyl)amino-4'-nitrostilbene and (IPDI) .
For the preparation of 4-di-(2-hydroxyethyl)amino-4'-nitrostilbene reference is made to EP-A1-0 350 112. Po1yurethane 3* was prepared by means of the above-described conventional polymerising method using this diol and isophorone diisocyanate.
Test samples were made of the prepared optically non-linear active polymers for use in Fabry-Perot experiments (r13) and crossed polariser experiments (r33-r13) in transmission. To this end a polyurethane layer provided between two planeparallel, semi-transparent metal electrodes was applied to a glass 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 millipore0 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.
WO 94tO1480 PCrtEP93/01587 ~139~71 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 Tg (180C and 200C, respectively) for 15 minutes~ The freezing in efficiency ~ (i.e., the ratio of the Pockels coefficient (r13) for a switched off DC-field after freezing in at room temperature to the Pockels coefficient for the switched on DC-field, r13 field off/r13 field on) is shown in TABLE 1, which also lists the Tg (measured by DSC~ and the Pockels coefficients (r33), it being assumed that r33 =~ 3 x r13. It proved possible to pole the film of polyurethane 3* at 140C in one minute.
The relaxation measurements were carried out at various temperatures.
The temperatures employed for polyurethane 1 and 2 were in the range of 100to 175C, for polyurethane 3* they were in the range of 100 to 135C. These values were plotted in an Arrhenius plot and from them the values of the half-life, i.e., the ttme 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 2a in TABLE 1.
TABLE I
~, _ . . ---25-polyurethan~ Tg r33 ~ t~
(oo) (pm7V) (%) (ho~r) at:
. _ 1 175 1,3 40 S,88 1,21 0,73 2 200 1,2 45 20,6 4,5 2,78 3~ ~--3* 140 2,2 60 0,0108 0,00027 0,00008C
_ The data shows that films prepared from the optically non-linear active polyurethanes according to the invention have a higher Tg than WO 94/01480 PCl'/EP93/0158i the already known optically non-linear active polyurethanes, and can be poled. In addition, the thermal stability of poled films containing polyurethanes according to the invention was found to be much higher at elevated temperatures such as 140-160C 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.
`- _ WO 94/01480 PCI'/EP93~01587 Dia~am_ 1 CHO
COOMe ¦1 + CS2+ ~)step 1 COOMe C~(OEt) 2 Ct:)OMe COOMe COOMe S ~ COOMe ~J ~COOMe ~COOMe [~ step 2 ~ [~ stel~ 3 CH(OEt)2 CXO
2 ~ ~ 4 CH20H -CH20Ac-- CH20H
~ CH20Ac ~ CH20 ~; _step 5 ~ ~ step 6 ~
N2 5 N2 6 ~2 5 SVBSTJTUTE SHEET
WO 94/01480 2 1 3 9 6 7 1 PCI`/EP93/01587 Diaqram 2 HO ~SOH AcO ~OAc AcO ~OAc steP 1 ~ N steP 2 ~ N
AcO ~OAc HO OH
step 3 ~ ~3 step 4 ~,PO(OEt) 4 NO2 ~ 6 :
SUBSTITUTE SHEEl-
Claims (8)
1. A non-linear optically active polyurethane comprising a polymeric main chain and a donor-.pi.-acceptor sidegroup, characterised in that the sidegroup comprises a rigid donor group which is bonded to the polymeric main chain as schematically depicted below:
wherein D represents a donor group, ? stands for a .pi.-system, A
is an acceptor group, and H is the main chain of the polyurethane.
wherein D represents a donor group, ? stands for a .pi.-system, A
is an acceptor group, and H is the main chain of the polyurethane.
2. A non-linear optically active polyurethane comprising a donor-.pi.-acceptor sidegroup, characterised in that it has a Tg above 170°C.
3. A non-linear optically active polyurethane comprising donor-.pi.-acceptor sidegroups, characterised in that it comprises a rigid donor group and has a Tg above 170°C.
4. A non-linear optically active polyurethane according to claim 1, characterised in that the rigid donor group is a nitrogen- or sulphur-containing alicyclic group.
16a
16a
5. A non-linear optically active polyurethane according to claim 4, characterised in that the nitrogen- or sulphur-containing alicylic group is dihydroxy-functionalised.
6. A non-linear optically active polyurethane according to claim 1, characterised in that the rigid donor group is a dihydroxy pyrrolidine group in which the nitrogen atom is directly coupled to the ?-acceptor group.
7. A non-linear optically active polyurethane according to claim 1, characterised in that the rigid donor group is a dihydroxy dichiafulvene group.
8. A dihydroxy-functionalised compound which acts as donor-?-acceptor group, characterised in that it satisfies formula 6 below:
formula 6 wherein X is -CR-=CR=-, -M=N-, -CR-=N- or -M=CR?-, Y is -CN, -NO2, CR-=C(CN)2, -CF3, -CCN=C(CN)2 or -SO2R2, R1 is -halogen, -R=, -OR2, -COR=, -CN or -CF3, -SO2R?
R2 is -H, or an alkyl group havig 1-3 carbon atoms, R3 is an alkyl or aryl group having 1-8 carbon atoms n is an integer from 0 to 4, and the X groups may be the same or different if n is greater than 1.
A non-linear optically active waveguide, characterised in that it comprises a non-linear optically active polyurethane according to any one of preceding claims 1-7.
formula 6 wherein X is -CR-=CR=-, -M=N-, -CR-=N- or -M=CR?-, Y is -CN, -NO2, CR-=C(CN)2, -CF3, -CCN=C(CN)2 or -SO2R2, R1 is -halogen, -R=, -OR2, -COR=, -CN or -CF3, -SO2R?
R2 is -H, or an alkyl group havig 1-3 carbon atoms, R3 is an alkyl or aryl group having 1-8 carbon atoms n is an integer from 0 to 4, and the X groups may be the same or different if n is greater than 1.
A non-linear optically active waveguide, characterised in that it comprises a non-linear optically active polyurethane according to any one of preceding claims 1-7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9201202 | 1992-07-06 | ||
| NL9201202 | 1992-07-06 | ||
| PCT/EP1993/001587 WO1994001480A1 (en) | 1992-07-06 | 1993-06-21 | Non-linear optically active polyurethanes having high glass transition temperatures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2139671A1 true CA2139671A1 (en) | 1994-01-20 |
Family
ID=19861019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002139671A Abandoned CA2139671A1 (en) | 1992-07-06 | 1993-06-21 | Non-linear optiically active polyurethanes having high glass transition temperatures |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0650502A1 (en) |
| JP (1) | JPH08501811A (en) |
| KR (1) | KR950702587A (en) |
| CN (1) | CN1083494A (en) |
| CA (1) | CA2139671A1 (en) |
| WO (1) | WO1994001480A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW296392B (en) * | 1993-09-29 | 1997-01-21 | Akzo Nobel Nv | |
| US5688896A (en) * | 1994-09-26 | 1997-11-18 | Akzo Nobel N.V. | Non-linear optically active polycarbonate |
| TW311990B (en) * | 1995-03-13 | 1997-08-01 | Akzo Nobel Nv | |
| EP0780722A1 (en) * | 1995-12-22 | 1997-06-25 | Akzo Nobel N.V. | Electro-optical device stable in the 600-1600 nanometer wavelength range |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68928746T2 (en) * | 1988-09-08 | 1999-03-11 | Akzo Nobel N.V., Arnheim/Arnhem | Integrated optical components |
| FR2636634B1 (en) * | 1988-09-16 | 1992-11-27 | Rhone Poulenc Chimie | POLYURETHANES, NON-LINEAR OPTICAL ACTIVE INGREDIENTS AND MATERIALS CONTAINING THE SAME, OPTICAL DEVICE CONTAINING THE SAME, AND METHODS OF MAKING SUCH COMPOUNDS AND MATERIALS |
| FR2646671B1 (en) * | 1989-05-03 | 1993-01-22 | Rhone Poulenc Chimie | ORGANIC MATERIAL ACTIVE IN NON-LINEAR OPTICS |
| DK0445864T3 (en) * | 1990-03-06 | 1994-11-07 | Akzo Nobel Nv | Thermally curable NLO system and integrated optical components made from this |
| EP0477666B1 (en) * | 1990-09-24 | 1995-06-28 | Siemens Aktiengesellschaft | Cross-linked epoxy-resins with non-linear optical properties |
-
1993
- 1993-06-21 JP JP6502871A patent/JPH08501811A/en active Pending
- 1993-06-21 EP EP93914688A patent/EP0650502A1/en not_active Withdrawn
- 1993-06-21 KR KR1019950700049A patent/KR950702587A/en not_active Withdrawn
- 1993-06-21 WO PCT/EP1993/001587 patent/WO1994001480A1/en not_active Ceased
- 1993-06-21 CA CA002139671A patent/CA2139671A1/en not_active Abandoned
- 1993-07-05 CN CN93108077A patent/CN1083494A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR950702587A (en) | 1995-07-29 |
| JPH08501811A (en) | 1996-02-27 |
| CN1083494A (en) | 1994-03-09 |
| WO1994001480A1 (en) | 1994-01-20 |
| EP0650502A1 (en) | 1995-05-03 |
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