Zhang Shujing, Ren Zhongjie, Sun Xiaoli, Li Huihui, Yan Shouke
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
Langmuir. 2017 Feb 7;33(5):1202-1209. doi: 10.1021/acs.langmuir.6b03924. Epub 2017 Jan 27.
In this study, the effect of composition and melting time on the phase separation of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blend thin films was investigated. Optical microscopy under phase contrast confirms the occurrence of phase separation of PHB/PPC blends at 190 °C. Polarized optical and scanning electron microscopies (POM and SEM) demonstrate that phase separation takes place along both horizontal and vertical film planes, which should be attributed to the two different interfaces and immiscible blends. A low PPC content (e.g. 30 wt %) results in the formation of compact PHB spherulites filling the whole space, whereas the noncrystallizable PPC spherical microdomains scatter in the PHB region, and their size shows a remarkable melting-time dependence. With the increasing PPC component and melting time, it is observed from POM that the separated PHB domains scattered in the continuous PPC phase, like the island structure. However, it can be revealed by SEM micrographs that the PHB thick domains are actually connected by its thin layer under the PPC layer. The real situation is, therefore, a large amount of PPC aggregates to the surface to form a network uplayer, whereas the PHB thick domains connected by its thin layer form a continuous PHB region, leading to a superimposed bilayer structure. There is also a small amount of PHB small domains scattered in the PHB phase. The PHB thick domains crystallize cooperatively with the PHB- or PHB-rich sublayer in a way just like the growth of pure PHB spherulites. This superimposed bilayer by interplay between phase separation and crystallization may provide availability to tailor the final structure and properties of crystalline/amorphous polymer blends.
在本研究中,研究了组成和熔融时间对聚(3-羟基丁酸酯)/聚(碳酸亚丙酯)(PHB/PPC)共混薄膜相分离的影响。相差光学显微镜证实了在190℃下PHB/PPC共混物发生相分离。偏光光学显微镜和扫描电子显微镜(POM和SEM)表明,相分离沿薄膜的水平和垂直平面发生,这应归因于两种不同的界面和不相容的共混物。低PPC含量(例如30 wt%)导致形成填充整个空间的致密PHB球晶,而非结晶的PPC球形微区分散在PHB区域,其尺寸表现出显著的熔融时间依赖性。随着PPC组分和熔融时间的增加,从POM观察到,分离的PHB区域分散在连续的PPC相中,呈岛状结构。然而,SEM显微照片显示,PHB厚区域实际上通过其在PPC层下的薄层相连。因此,实际情况是,大量PPC聚集到表面形成网络上层,而由其薄层连接的PHB厚区域形成连续的PHB区域,导致叠加双层结构。在PHB相中也有少量PHB小区域分散。PHB厚区域与PHB或富含PHB的亚层协同结晶,方式类似于纯PHB球晶的生长。这种通过相分离和结晶之间的相互作用形成的叠加双层结构可能为定制结晶/无定形聚合物共混物的最终结构和性能提供可能性。