Cyclodextrin-Induced Suppression of the Crystallization of Low-Molar-Mass Poly(ethylene glycol)

Ian W. Hamley*,  and , Valeria Castelletto, 
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Abstract

We examine the effect of alpha-cyclodextrin (αCD) on the crystallization of poly(ethylene glycol) (PEG) [poly(ethylene oxide), PEO] in low-molar-mass polymers, with Mw = 1000, 3000, or 6000 g mol–1. Differential scanning calorimetry (DSC) and simultaneous synchrotron small-/wide-angle X-ray scattering (SAXS/WAXS) show that crystallization of PEG is suppressed by αCD, provided that the cyclodextrin content is sufficient. The PEG crystal structure is replaced by a hexagonal mesophase of αCD-threaded polymer chains. The αCD threading reduces the conformational flexibility of PEG and, hence, suppresses crystallization. These findings point to the use of cyclodextrin additives as a powerful means to tune the crystallization of PEG (PEO), which, in turn, will impact bulk properties including biodegradability.

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环糊精对低摩尔质量聚乙二醇结晶的抑制作用
我们研究了α-环糊精(αCD)对低摩尔质量聚合物(Mw = 1000、3000 或 6000 g mol-1)中聚乙二醇(PEG)[聚环氧乙烷(PEO)]结晶的影响。差示扫描量热法(DSC)和同步辐射小角/广角 X 射线散射法(SAXS/WAXS)表明,只要环糊精含量足够,PEG 的结晶就会受到 αCD 的抑制。PEG 晶体结构被由αCD-螺纹聚合物链组成的六角介相取代。αCD 穿线降低了 PEG 的构象灵活性,从而抑制了结晶。这些发现表明,使用环糊精添加剂是调整 PEG(PEO)结晶的有力手段,而 PEG(PEO)的结晶反过来又会影响包括生物降解性在内的整体特性。
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