Clarification of effects of Dynamio Factors and Hydrogen Bonding in the Structure Formation Process for Main-Chain Liquid Crystalline Polymers

用DSC、偏光显微镜、固体~ 1C和~ 1 N NMR、广角X射线衍射等方法研究了由相同联苯基元和亚甲基间隔基元组成的主链型热致液晶聚氨酯（LCPU）和聚醚（LCPE）的氢键作用和影响结构形成过程的动力学因素<13><15>。详细的DSC测试结果表明，LCPU和LCPE的液晶和结晶过程存在很大差异，这可能是由于分子间NH-CO氢键的存在和不存在。在从熔体中结晶出来的样品中，过冷液晶组分以非晶组分的形式存在，两种样品中的液晶基元构象和液晶基元迁移率也有明显的不同，这表明LCPU在液晶态下通过分子间氢键形成了某种分子组装体。 ...更多信息 通过DSC分析，发现LCPE的液晶玻璃是由熔体在冰水中淬冷形成的。从这种类型的液态结晶玻璃中，β晶型主要通过在约60℃以下的温度下退火而结晶，而α晶型优先在较高温度下产生。此外，当稳定的β晶相在130℃下被冰水急冷时，结晶度更高的β晶型结晶出来。在此，通过在硅油浴中将液晶玻璃快速加热至130℃来产生这种稳定的液晶相，并且其结构似乎至少在两天内没有发生明显变化。目前正在对α型和β型以及稳定的β型进行详细的结构分析，以获得关于这两种形式的结晶机制的进一步信息，这些结晶机制与β型中分子链可能的重新取向有关。通过这些研究，将为真正控制液晶相分子链来开发高性能液晶高分子材料提供基础理论。少

Hydrogen bonding and dynamic factor affecting structure formation process habe been investigated for main-chain thermotropic liquid crystalline polyurethane(LCPU) and polyether(LCPE) composed of the same biphenylene mesogen and methylene spacer units by DSC, polarizing light microscopy, solid-state ^<13>C and ^<15>N NMR spectroscopy, and wide-angle X-ray diffractometry. Detailed DSC mesurements reveal that there are great differences in liquid crystallization and crystallization processes between LCPU and LCPE probably due to the presence and absence of intermolecular NH - CO hydrogen bonding. In the super-cooled liquid crystalline component, which exists as the noncrystalline component in the samples crystallized form the melt, the spacer conformation and mesogen mobility are also found tobe markedly different between the two samples.These facts suggest the formation of some kind of molecular assemblies through intermolecular hydrogen bonding in the liquid crystalline state for LCPU. … More On the basis of detailed DSC analyses, it is found that liquid crystalline glass is formed for LCPE by quenching from the melt to ice-water. From this type of the liquid crystailline glass, form β is mainly crystallized by annealing at temperatures lower about 60℃ while form α is preferentially produced at higher temperatures. Moreober, form β with much higher crystallinity is crystallized when the stable nematic phase at 130℃ is rapidly quenched to ice-water. Here, such a stable nematic phase is produced by rapidly heating the liquid crystalline glass to 130℃ in a silicone oil bath and no apparent change in its structure seems to occur at least for two days. Detailed structural analyses of forms α and β as well as the stable nematic phase are in progress to obtain further information about the crystallization mechanism of the two forms in relation to the possible reorientation of molecular chains in the nematic phase. Through these investigations basic theories will be proposed to develop high-performance liquid crystalline polymer materials by really controlling the molecular chains in the liquid crystalline phase. Less