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Studies on azobenzene chromophores content and its localization in functionalized poly(esterimide)s

Wanic A., Siwy M., Schab-Balcerzak E.

Polish Journal of Applied Chemistry

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2009

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Vol. 53, nr 4

277-294

EN

In this article determination of azobenzene chromophore content in poly(esterimide)s by 13C NMR spectroscopy was reported for the first time. Azopolymers were obtained by a posf-azo-coupling reaction. The chemical shifts of carbon atoms signal characteristic for evaluation of chromophores load level in polymers were established based on analysis of several proper compounds. It was found that the most important for such analysis are the ranges 147-155 ppm and 112-116 ppm in 13C NMR spectrum. The calculated degree of poly(estrimide)s dye functionalization was compared with results estimated from UV-Vis spectroscopy and were in good agreement. The obtained results led to conclusion that 13C NMR spectroscopy is useful tool for determination chromophore content and moreover its localization in polymer. The elaborated method could be applied not only for polymers investigated in this work but also for all polyimides functionalized by azobenzene derivatives.

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Novel Poly(etherimide)s with Attached NLO Moieties. I. Synthesis and Characterization

Schab-Balcerzak E.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 12

2293-2308

EN

Two types of novel poly(etherimide)s with attached photoresponsive azobenzene chromophores are presented. The polymers differing in the kind of linkage between the azobenzene units with the polymer chain, i.e. rigid and flexible, and in substituents on the chromophore moieties. The poly(etherimide)s with the rigidly incorporated the chromophores were synthesized from 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 2,4-diamino-4'-cyanoazobenzne and 2,4-diamino-4'-methylazobenzene. The polymers with the azobenzene chromophores, linked to the polymer backbone via long aliphatic spacers, were prepared from hydroxylpoly(etherimide) by the covalent bonding of new synthesized chromophores with the polymer backbone via the Mitsunobu reaction. The degree of functionalization of the poly(etherimide)s was estimated by UV-Vis and 1H NMR spectroscopies. The NLO polymers exhibited high glass transition temperatures (150-214 graduate C) and high thermal stability with decomposition temperatures in the range of 370-446 graduate C. The resulting polymers possessed good solubilities in common organic solvents. A dichroism up to 0.19 was induced in a chosen new synthesized poly(etherimide) (PEI 3).

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Holograficzne siatki dyfrakcyjne w funkcjonalizowanych poliamidoimidach

Schab-Balcerzak E.

Polimery

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2008

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T. 53, nr 9

663-669

PL

Przedstawiono podsumowanie wyników badań własnych dotyczących holograficznego zapisu siatek dyfrakcyjnych w serii poliamidoimidów (PAI) funkcjonalizowanych chromoforami azobenzenowymi. Polimery te różniły się budową łańcucha głównego, podstawnikami w grupie azobenzenowej, miejscem jej wprowadzenia do polimeru oraz zawartością chromoforu (schemat A). Holograficzny zapis siatek dyfrakcyjnych badano przy użyciu lasera Ar+ o długości linii 488 i 514,5nm. Pomiary wykonano w dwóch wariantach konfiguracji polaryzacji wiązek piszących: s-s i s-p. Wydajność dyfrakcji w badanych polimerach sięga 3,6%. Za pomocą mikroskopu sił atomowych (AFM) obserwowano tworzenie się siatek reliefowych charakteryzujących się regularną, sinusoidalną modulacją powierzchni. Omówiono zależność kinetyki zapisu siatek dyfrakcyjnych oraz głębokości modulacji powierzchni od budowy funkcjonalizowanych PAI.

EN

The paper recapitulates the results of own research concerning the holographic diffraction grating recording for series of polyamide imides (PAI) functionalized with azobenzene chromophores. The polymers differed in the backbone chain structure, in substituents in azobenzene group and this group position in the chain as well as in chromophore content (Scheme A, Table 2). Holographic diffraction grating recording was investigated using Ar+ laser beam at 488 and 514.5nm wavelength (Table 1, Fig. 1). The measurements were done at two variants of configurations of laser beam polarization i.e. s-s or s-p (Fig. 2). The polymers show diffraction efficiency up to 3.6% (Table 3 and 4). The formation of surface relief gratings (SRG), characterized by regular sinusoidal surface modulation, has been observed with use of atomic force microscopy (AFM) (Fig. 3 and 4). Dependences of kinetics of diffraction grating recording and the depth of surface modulation on PAI functionalization were discussed.