Huang He, Hu Yun, Zhang Jianming, Sato Harumi, Zhang Hongtao, Noda Isao, Ozaki Yukihiro
Department of Chemistry, School of Science and Technology and Research Center for Environmental Friendly Polymers, Kwansei-Gakuin University, Gakuen, Sanda 669-1337, Japan.
J Phys Chem B. 2005 Oct 20;109(41):19175-83. doi: 10.1021/jp0532162.
Miscibility and hydrogen-bonding interactions, as well as the morphological properties, of biodegradable polymer blends of poly(3-hydroxybutyrate) (PHB) and a 80% hydrolyzed poly(vinyl alcohol) (PVA80) were studied using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). It was found that PHB is miscible with PVA80 in the amorphous phase over the whole composition range. PVA80 or PHB assumes the amorphous state when its content in the blend is lower than 30 or 20 wt %, respectively. Due to the heavy overlapping of C=O stretching bands from both PVA80 and PHB and the nonmeasurable peak shift in the OH stretching band region, hydrogen-bonding interactions between the OH group of PVA80 and the C=O group of PHB were not detectable at room temperature, but were observed at a higher temperature of 180 degrees C. This is because hydrogen-bonding interactions are promoted above the melting points of these two crystalline polymers, by increasing the mixing entropy and reducing the Deltachi effect. Blending PHB with PVA80 does not have a significant effect on the OH groups of PVA80 that are hydrogen bonded with each other. Instead, the C=O groups of PHB dispossess some of the OH groups that are hydrogen bonded to the C=O groups of PVA80, which gives rise to the miscibility between PVA80 and PHB in the amorphous phase.
采用傅里叶变换红外光谱(FTIR)和差示扫描量热法(DSC)研究了聚(3-羟基丁酸酯)(PHB)与80%水解聚(乙烯醇)(PVA80)的生物可降解聚合物共混物的混溶性、氢键相互作用以及形态学性质。研究发现,在整个组成范围内,PHB与PVA80在非晶相中是可混溶的。当PVA80或PHB在共混物中的含量分别低于30 wt%或20 wt%时,它们呈非晶态。由于PVA80和PHB的C=O伸缩带严重重叠,且OH伸缩带区域的峰位移无法测量,因此在室温下未检测到PVA80的OH基团与PHB的C=O基团之间的氢键相互作用,但在180℃的较高温度下观察到了这种相互作用。这是因为在这两种结晶聚合物的熔点以上,通过增加混合熵和降低Δchi效应,促进了氢键相互作用。将PHB与PVA80共混对彼此形成氢键的PVA80的OH基团没有显著影响。相反,PHB的C=O基团取代了一些与PVA80的C=O基团形成氢键的OH基团,这导致了PVA80与PHB在非晶相中的混溶性。