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The conditions under which a given crystalline form of one of the two polymorphic phases of poly(decamethylene oxide) can be obtained have been investigated. In particular, the relationship between crystallization conditions, annealing behaviour and molecular weight and the formation of a given crystalline phase is discussed. The appearance of a stable monoclinic polytetrahydrofuran-type crystal form in poly(decamethylene oxide) turns out to be strongly temperature dependent in its formation and only occurs fully above 70°C.
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