Polymer morphology control with crystallization during polymerization

大多数天然聚合物在聚合时是结晶的。它们与聚合反应同时结晶。我们研究了溶液聚合过程中的结晶，以控制聚合物形态。1987年，我们发现并报道了在一定的聚合条件下可以形成针状的聚对氧苯甲酰基（POB）晶须，它是一种单链和伸展链晶体。这是第一个通过缩聚反应得到的聚合物晶须，为难加工聚合物的形态加工提供了一种新的方法。同时也揭示了POB晶须的形成机理。本论文主要研究了溶液聚合过程中结晶机理的基本问题，以控制聚合物的初生形态。研究了针状结晶的等温线形成机理、低聚物在堆积层中的固相聚合机理以及所用溶剂对低聚物结晶速率与形成速率的影响。最后，我们阐明了聚合条件对初生形态的影响。并将此方法应用于聚氧-2，6-萘二羰基和聚甲亚胺的合成，成功地合成了聚氧-2，6-萘二羰基晶须。因此，我们开发了结晶法与溶液聚合同时进行的聚合物形态控制。

Most natural polymers are crystalline when polymerized. They crystallize concurrently with the polymerization reaction. We have studied crystallization during solution polymerization to control polymer morphology. In 1987, we found and reported that needle-like poly (p-oxybenzoyl) (POB) whiskers, which were single and extended chain crystals could be formed under certain polymerization conditions. This was the first polymer whisker obtained by polycondensation reaction and showed a new morphological processing for intractable polymers. We have also manifested the formation mechanism of POB whiskers. In this study, we investigated the basic problems on mechanism of crystallization during solution polymerization to control the nascent morphology. The isothe formation mechanism of needle crystals, the solid state polymerization mechanism of oligomers in stacking lamella and the relation between formation rate and crystallization rate of oligomers by used solvents were studied. In final, we elucidated the influence for the nascent morphology'with polymerization conditions. Furthermore, we applied this method for poly (oxy-2, 6-naphthalenediyl carbonyl) and poly (azomethine) and succeeded in the synthesis of the whisker. Thus, we developed the morphology control of polymers by crystallization method concurrent with solution polymerization.