Herald of Technological University Herald of Technological University ВЕСТНИК ТЕХНОЛОГИЧЕСКОГО УНИВЕРСИТЕТА 3034-4689 62257 СТРУКТУРА ВЕЩЕСТВА И ТЕОРИЯ ХИМИЧЕСКИХ ПРОЦЕССОВ СТРУКТУРА ВЕЩЕСТВА И ТЕОРИЯ ХИМИЧЕСКИХ ПРОЦЕССОВ Segmental Mobility in Crystalline Poly(3-hydroxybutyrate) Studied by EPR Probe Technique Iordanskii A L Iordanskii A L Kamaev P P Kamaev P P Karpova S G Karpova S G Olkhov A A Olkhov A A Zernova Yu N Zernova Yu N Zaikov G E Zaikov G E ov_stoyanov@mail.ru N.N.Semenov’s Institute of Chemical Physics ru N.N.Semenov’s Institute of Chemical Physics ru N.N.Semenov’s Institute of Chemical Physics ru N.N.Semenov’s Institute of Chemical Physics ru N.M.Emanuel’s Institue of Biochemical Physics, RAS ru N.M.Emanuel’s Institue of Biochemical Physics, RAS ru N.N.Semenov’s Institute of Chemical Physics ru N.N.Semenov’s Institute of Chemical Physics ru N.N.Semenov’s Institute of Chemical Physics ru N.N.Semenov’s Institute of Chemical Physics ru Kazan National Research Technological University ru Kazan National Research Technological University ru 01 08 2025 01 08 2025 17 1 24 27 20 04 2023 https://vestniktu.ru/en/nauka/article/62257/view

Методом ЭПР изучена молекулярная подвижность поли (3- оксибутирата ) (ПГБ) в интервале температур от 20 до 90 °С с использованием стабильных нитроксильных радикалов 2,2,6,6-тетраметил-1-пиперидинилокси (Tempo) и 4-гидрокси-2,2,6,6- тетраметил-1- пиперидинилокси (Tempol) в качестве спиновых зондов. Две серии образцов ПГБ, полученные разными методами, обладали изотропной и текстурированной морфологией. Некристаллическая фаза ПГБ содержит области двух типов с заметно различающейся молекулярной подвижностью. Предполагается, что "плотные" области, характеризующиеся сравнительно низкой подвижностью полимерных цепей, находятся вблизи поверхности кристаллических зерен, в то время как "свободные" (аморфные) области с более высокой подвижностью цепей более отдалены от поверхности зерен. Молекулярная подвижность в плотных областях практически одинакова для обоих изотропного и текстурированного образцов ПГБ, а подвижность в рыхлых областях в изотропном образце ниже, чем в текстурированном. Насыщение полимера водяным паром зависит как от подвижности полимерных цепей, так и относительного содержания “свободных” и плотных областей в образцах.

The molecular mobility of poly(3-hydroxybutyrate) (PHB) was studied in the temperature interval from 20 to 90 °C by EPR using stable nitroxyl radicals 2,2,6,6-tetramethyl-1-piperidinyloxy (Tempo) and 4-hydroxy-2,2,6,6-tetramethyl-1- piperidinyloxy (Tempol) as spin probes. Two series of PHB samples, prepared by different methods, possessed isotropic and textured morphologies. The noncrystalline phase of PHB contain regions of two types with markedly different molecular mobilities. It is suggested that “dense” regions, characterized by a comparatively low mobility of polymer chains, are located near the surface of crystalline grains, while the “loose” (amorphous) regions with a higher mobility of chains are more distant from the surface of grains. Molecular mobility in the dense regions was virtually the same for both isotropic and textured PHB samples, whereas the mobility in the loose regions was lower in the isotropic samples than in the textured ones. Saturation of the polymer with water vapor affected both the mobility of polymer chains and the relative content of loose and dense regions in the samples.

 poly(3-hydroxybutyrate) molecular mobility EPR поли(3-гидроксибутират) молекулярная подвижность ЭПР poly(3-hydroxybutyrate) molecular mobility EPR поли(3-гидроксибутират) молекулярная подвижность ЭПР

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