Polymer morphology control with crystallization during polymerization

大多数天然聚合物在聚合时都是结晶的。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过程，以控制聚合物的形态。1987年，我们发现并报道了在一定的聚合条件下可以形成单链的针状聚对氧苯甲酰基(POB)晶须。这是第一个通过缩聚反应获得的聚合物晶须，展示了难熔聚合物的一种新的形态加工方法。我们还揭示了POB晶须的形成机理。在本研究中，我们研究了溶液聚合过程中结晶机理的基本问题，以控制初生形态。研究了针状晶的形成机理、低聚物在堆积片层中的固相聚合机理以及所用溶剂中低聚物的形成速度与结晶速度的关系。最后，我们阐明了聚合条件对初生形态的影响。此外，我们还将该方法应用于聚(氧-2，6-萘二酰基)和聚甲亚胺的合成，并成功地合成了晶须。因此，我们发展了同时进行溶液聚合的结晶法来控制聚合物的形态。

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.