PL213407B1 - New photochromic ethoxysilane precursor and method of its manufacturing and application as the photochromic material - Google Patents
New photochromic ethoxysilane precursor and method of its manufacturing and application as the photochromic materialInfo
- Publication number
- PL213407B1 PL213407B1 PL386812A PL38681208A PL213407B1 PL 213407 B1 PL213407 B1 PL 213407B1 PL 386812 A PL386812 A PL 386812A PL 38681208 A PL38681208 A PL 38681208A PL 213407 B1 PL213407 B1 PL 213407B1
- Authority
- PL
- Poland
- Prior art keywords
- amino
- ethyl
- methyl
- phenyl
- nitro
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- 239000002243 precursor Substances 0.000 title claims description 10
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 title claims description 6
- 239000000463 material Substances 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 title 1
- -1 triethoxysilyl Chemical group 0.000 claims description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- MIHADVKEHAFNPG-UHFFFAOYSA-N 2-Amino-5-nitrothiazole Chemical class NC1=NC=C([N+]([O-])=O)S1 MIHADVKEHAFNPG-UHFFFAOYSA-N 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 9
- GHDZRIQTRDZCMV-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-[(4-nitrophenyl)diazenyl]anilino]ethanol Chemical compound C1=CC(N(CCO)CCO)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 GHDZRIQTRDZCMV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FOQABOMYTOFLPZ-UHFFFAOYSA-N 2-[n-ethyl-4-[(4-nitrophenyl)diazenyl]anilino]ethanol Chemical compound C1=CC(N(CCO)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 FOQABOMYTOFLPZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VIIZJXNVVJKISZ-UHFFFAOYSA-N 2-(n-methylanilino)ethanol Chemical compound OCCN(C)C1=CC=CC=C1 VIIZJXNVVJKISZ-UHFFFAOYSA-N 0.000 description 1
- KQIKKETXZQDHGE-FOCLMDBBSA-N 4,4'-diaminoazobenzene Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=C(N)C=C1 KQIKKETXZQDHGE-FOCLMDBBSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- FKPXGNGUVSHWQQ-UHFFFAOYSA-N 5-methyl-1,2-oxazol-3-amine Chemical compound CC1=CC(N)=NO1 FKPXGNGUVSHWQQ-UHFFFAOYSA-N 0.000 description 1
- VVVCJCRUFSIVHI-UHFFFAOYSA-N 5-nitro-1,3-thiazole Chemical compound [O-][N+](=O)C1=CN=CS1 VVVCJCRUFSIVHI-UHFFFAOYSA-N 0.000 description 1
- FOQABOMYTOFLPZ-ISLYRVAYSA-N Disperse Red 1 Chemical compound C1=CC(N(CCO)CC)=CC=C1\N=N\C1=CC=C([N+]([O-])=O)C=C1 FOQABOMYTOFLPZ-ISLYRVAYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical class O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku jest pochodna 2-amino-5-nitrotiazolu oraz sposób jej wytwarzania oraz zastosowanie jako materiału fotochromowego do otrzymywania metodą zol-żel cienkich warstw.The subject of the invention is a 2-amino-5-nitrothiazole derivative and a method of its preparation and the use as a photochromic material for the preparation of the sol-gel method of thin films.
Z literatury znane są hybrydowe materiały polisiloksanowe o właściwościach fotochromowych i nieliniowych optycznie. Znacząca ich większość dotyczy jednak materiałów, będących pochodnymi takich barwników jak N-etylo-N-(2-hydroksyetylo)-4-(4-nitrofenyloazo)aniliny (Disperse Red 1) i N,N-di(2-hydroksyetylo)-4-(4-nitrofenyloazo)aniliny (Disperse Red 19). W publikacjach Y. Cui, M. Wang,The literature describes hybrid polysiloxane materials with photochromic and optically nonlinear properties. The vast majority of them, however, concern materials derived from such dyes as N-ethyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline (Disperse Red 1) and N, N-di (2-hydroxyethyl) -4 - (4-nitrophenylazo) aniline (Disperse Red 19). In the publications of Y. Cui, M. Wang,
L. Chen. G. Qian, Dyes and Pigments 62 (2004) 43-47; F. Chaumel, H. Jiang, A. Kakkar, Chemical Materials 13 (2001) 3389-3395; I.G. Marino, D. Bersani, P.P Lottici, Optical Materials 15 (2001) 279-284; D.H. Choi, K.J. Cho, Y.K. Cha, S.J. Oh, Bulletin of Korean Chemical Society 21 (2000) 1222-1226; D. Riehl, F. Chaput, Y. Levy, J.-P. Boilot, F. Kajzar, P.-A. Chollet, Chemical Physics Letters 245 (1995) 36-40, zostały opisane sposoby otrzymywania i właściwości materiału hybrydowego opartego na N-etylo-N-(2-hydroksyetylo)-4-(4-nitrofenyloazo)anilinie. W publikacjach takich jak:L. Chen. G. Qian, Dyes and Pigments 62 (2004) 43-47; F. Chaumel, H. Jiang, A. Kakkar, Chemical Materials 13 (2001) 3389-3395; I.G. Marino, D. Bersani, P.P. Lottici, Optical Materials 15 (2001) 279-284; D.H. Choi, K.J. Cho, Y.K. Cha, S.J. Oh, Bulletin of Korean Chemical Society 21 (2000) 1222-1226; D. Riehl, F. Chaput, Y. Levy, J.-P. Boilot, F. Kajzar, P.-A. Chollet, Chemical Physics Letters 245 (1995) 36-40, methods for the preparation and properties of the hybrid material based on N-ethyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline have been described. In publications such as:
M.R. Kim, Y.-I. Choi, S.W. Park, J.-W. Lee, J.-K. Lee, Dyes and Pigments 70 (2006) 171-176; H. Zhang, D. Lu, M. Fallahi, Optical Materials 28 (2006) 992-999 i P.-H. Sung. T.-F. Llsu, Polymer 39 (1998) 1453-1459 przedstawiono metody otrzymywania hybrydowych pochodnych N,N-di-(2-hydroksyetylo)-4-(4-nitrofenyloazo)aniliny. Z kolei w publikacji Y. Cui, G. Qian, L. Chen, Z. Wang, J. Gao, M. Wang, Journal of Physical Chemistry B 110 (2006) 4105-4110, opisano metodę otrzymywania hybrydowych filmów zawierających pochodną benzotiazolu. Hybrydowa pochodna 2-amino-5-nitrotiazolu otrzymana w reakcji z 2-[metylo(fenylo)amino)etanolem jest przedmiotem publikacji Y. Cui, G. Qian L. Chen, Z. Wang, M. Wang, Dyes and Pigments 77 (2008) 217-222.M.R. Kim, Y.-I. Choi, S.W. Park, J.-W. Lee, J.-K. Lee, Dyes and Pigments 70 (2006) 171-176; H. Zhang, D. Lu, M. Fallahi, Optical Materials 28 (2006) 992-999 and P.-H. Sung. T.-F. Llsu, Polymer 39 (1998) 1453-1459 methods for the preparation of hybrid N, N-di- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline derivatives are presented. In turn, the publication of Y. Cui, G. Qian, L. Chen, Z. Wang, J. Gao, M. Wang, Journal of Physical Chemistry B 110 (2006) 4105-4110 describes a method of obtaining hybrid films containing a benzothiazole derivative. A hybrid derivative of 2-amino-5-nitrothiazole obtained by reaction with 2- [methyl (phenyl) amino) ethanol is the subject of the publication by Y. Cui, G. Qian L. Chen, Z. Wang, M. Wang, Dyes and Pigments 77 ( 2008) 217-222.
Inne organiczno-nieorganiczne materiały hybrydowe, zawierające ugrupowania azobenzenowe. będące pochodnymi, odpowiednio, sulfametoksazolu oraz 4-aminobenzonitrylu znane są z publikacji:Other organic-inorganic hybrid materials containing azobenzene groups. being derivatives of sulfamethoxazole and 4-aminobenzonitrile, respectively, are known from the publication:
M. Serwadczak, S. Kucharski Journal of Sol-Gel Science and Technology 37 (2006) 57-62 i S. Kucharski, R. Janik. Optical Materials 27 (2005) 1637-1641. Z polskiego zgłoszenia patentowego nr P.382162 znany jest etoksysilanowy prekursor pochodny 3-amino-5-metyloizoksazolu, stosowany jako materiał fotochromowy. W publikacji N. Liu, D.R. Dunphy, M.A. Rodriguez, S. Singer, J. Brinker Chemical Communication 10 (2003) 1144-1145 opisano syntezę i izomeryzację ugrupowania azobenzenowego w materiałach hybrydowych opartych na 4-fenyloazoanilinie zaś syntezę i izomeryzację ugrupowania azobenzenowego w materiałach hybrydowych opartych na 4,4'-azodianilinie w publikacjiM. Serwadczak, S. Kucharski Journal of Sol-Gel Science and Technology 37 (2006) 57-62 and S. Kucharski, R. Janik. Optical Materials 27 (2005) 1637-1641. The Polish patent application no. P.382162 describes an ethoxysilane precursor derived from 3-amino-5-methylisoxazole, used as a photochromic material. In the publication of N. Liu, D.R. Dunphy, M.A. Rodriguez, S. Singer, J. Brinker Chemical Communication 10 (2003) 1144-1145 describes the synthesis and isomerization of the azobenzene moiety in 4-phenylazoaniline-based hybrid materials and the synthesis and isomerization of the azobenzene moiety in 4,4'-azodianiline-based hybrid materials in publication
N. Liu, K. Yu, B. Smarsly, D.R. Dunphy, Y.-B. Jiang, C.J. Brinker, Journal of American Chemical Society 124 (2002) 14540-14541.N. Liu, K. Yu, B. Smarsly, D.R. Dunphy, Y.-B. Jiang, C.J. Brinker, Journal of the American Chemical Society 124 (2002) 14540-14541.
Nie są znane etoksy silanowe prekursory materiałów hybrydowych pochodne 2-amino-5-nitrotiazolu o wzorze 1, będące przedmiotem wynalazku.The ethoxy silane precursors of the 2-amino-5-nitrothiazole derivatives of the formula I, which are the subject of the invention, are not known.
Istotę wynalazku stanowi pochodna 2-amino-5-nitrotiazolu, którą stanowi N-[3-(trietoksysililo)propylo]karbaminian 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etylu o wzorze 1, zawierający ugrupowanie heterocykliczne i etylowy łańcuch pomiędzy atomem azotu grupyThe essence of the invention is the 2-amino-5-nitrothiazole derivative, which is 2- [methyl N- [3- (triethoxysilyl) propyl] carbamate ({4 - [(E) -2- (5-nitro-1,3-thiazole) -2-yl) diazen-1-yl] phenyl}) amino] ethyl of the formula 1, containing a heterocyclic moiety and an ethyl chain between the nitrogen atom of the group
N-metylowej ugrupowania chromoforowego i atomem tlenu wiązania uretanowego.The N-methyl chromophore moiety and the oxygen atom of the urethane bond.
Nowa pochodna 2-amino-5-nitrotiazolu, dzięki obecności grupy azowej, jest materiałem fotochromowym i charakteryzuje się położeniem maksimum absorpcji przy ok. 565 nm, czyli pasmo absorpcji przesunięte jest w kierunku fal dłuższych w porównaniu do znanych w literaturze etoksysialanowych prekursorów pochodnych N-etylo-N-(2-hydroksyetylo)-4-(4-nitrofenyloazo)aniliny i N,N-di-(2-hydroksyetylo)-4-(4-nitrofenyloazo)aniliny.The new derivative of 2-amino-5-nitrothiazole, due to the presence of the azo group, is a photochromic material and is characterized by the absorption maximum at approx. 565 nm, i.e. the absorption band is shifted towards longer wavelengths compared to the ethoxysialate precursors of N- known in the literature. ethyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) anilines and N, N-di- (2-hydroxyethyl) -4- (4-nitrophenylazo) anilines.
Sposób wytwarzania pochodnej 2-amino-5-nitrotiazolu, którą stanowi N-[3-(trietoksysililo)propylo]karbaminian 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etylu, o wzorze 1, polega na reakcji addycji 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etanolu z izocyjanianem 3-(trietoksysililo)propylu, w rozpuszczalniku takim jak tetrahydrofuran lub pirydyna w obecności katalizatora, wybranego z grupy obejmującej trietyloaminę lub dilaurynian dibutylocyny.Preparation of the 2-amino-5-nitrothiazole derivative which is 2- [methyl N- [3- (triethoxysilyl) propyl] carbamate ({4 - [(E) -2- (5-nitro-1,3-thiazol- 2-yl) diazen-1-yl] phenyl}) amino] ethyl, of formula 1, relies on the addition reaction of 2- [methyl ({4 - [(E) -2- (5-nitro-1,3-thiazole -2-yl) diazen-1-yl] phenyl}) amino] ethanol with 3- (triethoxysilyl) propyl isocyanate, in a solvent such as tetrahydrofuran or pyridine in the presence of a catalyst selected from the group consisting of triethylamine or dibutyltin dilaurate.
Otrzymany w wyniku reakcji etoksysilanowy prekursor fotochromowy, w postaci N-[3-(trietoksysililo)propylo]karbaminianu 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etylu wytrąca się z mieszaniny reakcyjnej w suchym n-heksanie.The ethoxysilane photochromic precursor obtained by the reaction, in the form of 2- [methyl N- [3- (triethoxysilyl) propyl] carbamate ({4 - [(E) -2- (5-nitro-1,3-thiazol-2-yl) ) diazen-1-yl] phenyl}) amino] ethyl is precipitated from the reaction mixture in dry n-hexane.
Istotą wynalazku jest również zastosowanie N-[3-(trietoksysililo)propylo]karbaminianu 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etylu, o wzorze 1, do wytwarzania cienkich transparentnych twardych filmów hybrydowych metodą zol-żel, bezpośrednio z mieszaniny reakcyjnej. W celu otrzymania filmu hybrydowego, etoksysilanowy prekursor fotochromowy o wzorze 1The essence of the invention is also the use of 2- [methyl ({4 - [(E) -2- (5-nitro-1,3-thiazol-2-yl) diazen-1-] carbamate N- [3- (triethoxysilyl) propyl] carbamate. yl] phenyl}) amino] ethyl, of formula 1, for the preparation of thin transparent hard hybrid films by sol-gel method directly from the reaction mixture. In order to obtain a hybrid film, the ethoxysilane photochromic precursor of formula 1
PL 213 407 B1 miesza się z drugim prekursorem w postaci tetraetyloortosilanu, użytym w ilości od 85 do 97% wagowych oraz bezwodnym etanolem, w temperaturze pokojowej i poddaje się hydrolizie kwasowej z użyciem katalizatora w postaci kwasu solnego, a następnie z mieszaniny reakcyjnej formuje się cienkie warstwy. Przy czym bezwodny etanol stosuje się jako homogenizator, korzystnie w czterokrotnym nadmiarze w stosunku do sumy mas obu prekursorów.The PL 213 407 B1 is mixed with the second tetraethylorthosilane precursor used in an amount of 85 to 97% by weight and anhydrous ethanol at room temperature and subjected to acid hydrolysis with a hydrochloric acid catalyst, and then thinning from the reaction mixture. layers. Anhydrous ethanol is used as a homogenizer, preferably in a fourfold excess with respect to the sum of the weights of both precursors.
Otrzymane z etoksysilanowych prekursorów fotochromowych zgodnie z wynalazkiem transparentne, twarde filmy mają właściwości nieliniowo-optyczne i fotochromowe oraz znajdują zastosowanie w optoelektronice i optyce nieliniowej, a także w optycznym zapisie informacji.The transparent hard films obtained from the ethoxysilane photochromic precursors according to the invention have nonlinear-optical and photochromic properties and are used in optoelectronics and non-linear optics, as well as in the optical recording of information.
Przedmiot wynalazku przedstawiony jest w przykładzie wytwarzania N-[3-(trietoksysililo)propylo]karbaminianu 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etylu o wzorze 1 oraz w dwóch przykładach zastosowania związku o wzorze 1, do otrzymywania transparentnych filmów hybrydowych.The invention is described in an example for the preparation of 2- [methyl ({4 - [(E) -2- (5-nitro-1,3-thiazol-2-yl) diazene- 1-yl] phenyl}) amino] ethyl of the formula 1 and in two examples of the use of the compound of the formula 1 for the preparation of transparent hybrid films.
P r z y k ł a d IP r z k ł a d I
W celu otrzymania N-[3-(trietoksysililo)propylo]karbaminianu 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etylu, o wzorze 1, w kolbie okrągłodennej o pojemności 15 ml umieszcza się 0,22 mmola (0,068 g) 2-[metylo({4-[(E)-2-(5-nitro-1,3-tiazol-2-ilo)diazen-1-ilo]fenylo})amino]etanolu i rozpuszcza się w 2,3 ml tetrahydrofuranu. Następnie dodaje się 0,5 mmola (0,12 g) izocyjanianu 3-(trietoksysilylo)propylu i całość miesza się 10 min w temperaturze pokojowej przedmuchując suchym azotem. Po dodaniu katalitycznej ilości dilaurynianu dibutylocyny ogrzewa się w atmosferze azotu przez 24 godziny w temperaturze 80°C. Po tym czasie w celu wydzielenia produktu o wzorze 1, mieszaninę reakcyjną wylewa się do suchego n-heksanu. Wytrącony osad przemywa się kilkakrotnie n-heksanem, a następnie suszy się w suszarce w temperaturze ok. 60°C. Wydajność wynosi 67%.To obtain 2- [methyl ({4 - [(E) -2- (5-nitro-1,3-thiazol-2-yl) diazen-1-yl] carbamate N- [3- (triethoxysilyl) propyl] carbamate phenyl}) amino] ethyl of the formula I in a 15 mL round bottom flask is placed 0.22 mmol (0.068 g) of 2- [methyl ({4 - [(E) -2- (5-nitro-1, 3-thiazol-2-yl) diazen-1-yl] phenyl}) amino] ethanol and dissolved in 2.3 ml of tetrahydrofuran. Then 0.5 mmol (0.12 g) of 3- (triethoxysilyl) propyl isocyanate are added and the mixture is stirred for 10 min at room temperature while purging with dry nitrogen. After addition of a catalytic amount of dibutyltin dilaurate, it is heated under nitrogen for 24 hours at 80 ° C. After this time, the reaction mixture was poured into dry n-hexane to isolate the product of Formula 1. The precipitate formed is washed several times with n-hexane and then dried in an oven at a temperature of about 60 ° C. The yield is 67%.
FTIR, (KBr, cm-1): 3325 (γ (N-H), m); 3078 (γ (CacH, vw); 2961 (Vas (-CH3), m); 2710 (γ (-CH3), grupy N-metylowej); 1720 (v (C=O), s); 1606 (γ (C=C) grupy fenylowej -C6H4; 1541 (vas (-NO2), s); 1508 (ó(N-H), s); 1471 (ó(-CH2-), w); 1397 (δ (-CH3), w); 1332 (Vs (-NO), s); 1259 (v (N=N), w); 1065 (v (C-H), grup etoksylowych przy Si-O-C, vs); 955 (vs (Si-O-C), m); 828 (γ (CAr-H), od para podstawionego pierścienia fenylowego, s) 1HNMR (300 Hz, rozpuszczalnik DMSO-d6, TMS, ppm): 0,45 (t, 2H, -CH2CH2CH2-); 1,06 (m, 9H, -OCH2CH3); 1,36 (d, 2H, -CH2CH2CH2-); 2,92 (d, 2H, -CH2CH2CH2-); 3,23 (s, 3H, -NCH3); 3,45 (t, 6H, -OCH2CH3); 3,90 (t, 2H, - CH2N-); 4,29 (t, 2H, -CH2O-); 7,05 (d, 2H, protony pierścienia fenylowego w pozycji orto w stosunku do grupy aminowej); 7,18 (s, 1H, NH); 7,88 (d, 2H, protony pierścienia fenylowego w pozycji meta w stosunku do grupy aminowej); 8,83 (s, 1H, proton pierścienia tiazolowego).FTIR, (KBr, cm -1 ): 3325 (γ (NH), m); 3078 (γ (CacH, vw); 2961 (Vas (-CH3), m); 2710 (γ (-CH3), N-methyl group); 1720 (v (C = O), s); 1606 (γ ( C = C) phenyl group -C 6 H 4 ; 1541 (v as (-NO2), s); 1508 (ó (NH), s); 1471 (ó (-CH2-), w); 1397 (δ ( -CH3), w); 1332 (Vs (-NO), s); 1259 (v (N = N), w); 1065 (v (CH), ethoxyl groups at Si-OC, vs); 955 (vs (Si-OC), m); 828 (γ (CAr-H), from para substituted phenyl ring, s) 1 HNMR (300 Hz, solvent DMSO-d6, TMS, ppm): 0.45 (t, 2H, -CH2CH2CH2-); 1.06 (m, 9H, -OCH2CH3); 1.36 (d, 2H, -CH2CH2CH2-); 2.92 (d, 2H, -CH2CH2CH2-); 3.23 (s, 3H , -NCH3); 3.45 (t, 6H, -OCH2CH3); 3.90 (t, 2H, - CH2N-); 4.29 (t, 2H, -CH2O-); 7.05 (d, 2H , protons of the phenyl ring in the position ortho to the amino group); 7.18 (s, 1H, NH); 7.88 (d, 2H, protons of the phenyl ring in the meta position in relation to the amino group); 8.83 ( s, 1H, thiazole ring proton).
P r z y k ł a d IIP r z x l a d II
W celu otrzymania cienkich filmów postępuje się jak w przykładzie I, z tą różnicą, że po 24 godzinach reakcji mieszaniny nie wylewa się do n-heksanu, dodaje się natomiast 1,7 mmola (0,35 g) tetraetyloortosilanu i 43,41 mmol (2,00 g) bezwodnego etanolu. Po 10 minutach mieszania do układu wkrapla się powoli 8,33 mmol (0,15 g) wody i 0,1 mmol (3,6 mg) HCl jako katalizator. Mieszanie kontynuuje się przez 45 minut w temperaturze pokojowej. Bezpośrednio przed przygotowaniem filmów mieszaninę filtruje się przy użyciu filtrów (0,2 pm) i następnie metodą „spin-coating” formuje się cienkie, transparentne filmy na płytkach szklanych. Tak otrzymane filmy utwardza się w temperaturze 80°C (przez 2 godziny), a następnie w temperaturze 120°C (przez kolejną godzinę). Pasmo maksimum absorpcji, Amax, tak przygotowanych filmów wynosi 565 nm.The procedure for obtaining thin films was as in Example 1, except that after 24 hours of reaction, the mixture was not poured into n-hexane, instead 1.7 mmol (0.35 g) of tetraethylorthosilane and 43.41 mmol ( 2.00 g) anhydrous ethanol. After 10 minutes of stirring, 8.33 mmol (0.15 g) of water and 0.1 mmol (3.6 mg) of HCl catalyst are slowly added dropwise to the system. Stirring is continued for 45 minutes at room temperature. Immediately before preparing the films, the mixture is filtered using filters (0.2 µm) and then, using the "spin-coating" method, thin, transparent films are formed on glass plates. The films thus obtained are hardened at a temperature of 80 ° C (for 2 hours) and then at a temperature of 120 ° C (for another hour). The band of maximum absorption, A max , of the films prepared in this way is 565 nm.
P r z y k ł a d IIIP r z x l a d III
Postępuje się tak jak w przykładzie II, z tą różnicą, że substraty reakcji addycji rozpuszcza się w bezwodnej pirydynie, a jako katalizator stosuje się kilka kropel trietyloaminy.The procedure is as in Example 2, with the difference that the addition reactants are dissolved in anhydrous pyridine and a few drops of triethylamine are used as the catalyst.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL386812A PL213407B1 (en) | 2008-12-15 | 2008-12-15 | New photochromic ethoxysilane precursor and method of its manufacturing and application as the photochromic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL386812A PL213407B1 (en) | 2008-12-15 | 2008-12-15 | New photochromic ethoxysilane precursor and method of its manufacturing and application as the photochromic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL386812A1 PL386812A1 (en) | 2010-06-21 |
| PL213407B1 true PL213407B1 (en) | 2013-02-28 |
Family
ID=42990557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL386812A PL213407B1 (en) | 2008-12-15 | 2008-12-15 | New photochromic ethoxysilane precursor and method of its manufacturing and application as the photochromic material |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL213407B1 (en) |
-
2008
- 2008-12-15 PL PL386812A patent/PL213407B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL386812A1 (en) | 2010-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103328526B (en) | Photopolymer formulations for the preparation of holographic media | |
| US9804490B2 (en) | Holographic media with improved light sensitivity | |
| EP3733784B1 (en) | Photopolymer composition | |
| CN103222000A (en) | Photopolymer formulation for producing holographic media having highly cross-inked matrix polymers | |
| KR102239212B1 (en) | Photopolymer composition | |
| CN103842334A (en) | Intermediate for manufacture of polymerizable compound and process for manufacture thereof | |
| US11760765B2 (en) | Method for producing triarylorganoborates | |
| JPH10324690A (en) | Photocrosslinkable silane derivative | |
| KR20160072158A (en) | Photopolymer formulation for production of holographic media comprising borates with low tg | |
| CN102666469A (en) | Novel non-crystalline methacrylate, its preparation and application | |
| JP6359379B2 (en) | Colorant compound | |
| PL213407B1 (en) | New photochromic ethoxysilane precursor and method of its manufacturing and application as the photochromic material | |
| JPH09501959A (en) | Crosslinkable polymers, especially for optical and non-linear optical applications, materials or devices using the same, and methods for making the polymers | |
| PL214096B1 (en) | New non-linear optical photochromic monomer, method of its manufacturing and application of the non-linear optical photochromic monomer | |
| González-Lainez et al. | Using functionalized nonlinear optical chromophores to prepare NLO-active polycarbonate films | |
| KR101598545B1 (en) | Polyamide-based photoreactive polymer and preparation method thereof | |
| JP2856926B2 (en) | Organosilicon compound | |
| PL212460B1 (en) | New hybrid derivative of 3-amino 5-methyloisoxazol and the manner of its production and application as photo-chromium material | |
| CN106103552B (en) | Cellulose ester film, polarizer and liquid crystal display device | |
| TWI820340B (en) | Resin materials for making three-dimensional objects and methods of using the same | |
| FR2661416A1 (en) | Optionally oriented organic material active in nonlinear optics and process for its preparation | |
| PL214617B1 (en) | Photochromic N-[4-[(E)-phenylazo]phenyl]sulfonylobenzamide dyes and process for the preparation thereof | |
| CN121181524A (en) | Dendritic (meth)acrylate monomers, holographic recording media, preparation methods and related apparatus | |
| TW202413538A (en) | Compound, composition, film, laminate, and display device | |
| JP2003005325A (en) | Optical recording material and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20111215 |