High-performance polymeric materials with good processability and enhanced performance (higher thermal stability and mechanical strength, higher glass transition temperature (T_g) and lowered thermal expansion) have long been explored by scientists and engineers. The present study demonstrated a new way to fabricate high-performance polymers, such as polyarylamide (traditional polyarylamides can’t be processed by melt processing due to the lack of viscous flow temperature before thermal decomposition), with excellent processability via a facile two-step process, i.e. low-temperature melt processing and a subsequent in-situ thermal curing. Through designing the structure of the BCB-containing precursors, we can well control the melting point and curing temperature, thus adjust the melt processing temperature and curing temperature of the polymers. In our experiments, the temperature difference between precursor melting point and polymerization temperature can be over 200 °C, providing wide processing window and long storage lifetime. Besides, these precursors also possess excellent solubility in organic solvents, which endow them with the possibility of solution or melt processing, as illustrated by the representative precursor, DODA-BCB. The obtained polymer resin films show good thermal stability (T_d,5% > 410 °C), high glass transition temperatures (T_g > 240 °C) and good mechanical strength (storage modulus > 1.8 GPa). Further studies on the thermal expansion behavior of the films reveal the thermal contracting feature of p-3,4′-ODA-BCB, the mechanism has been discussed in detail using DFT calculations, VT-FTIR and TMA.

高性能聚合物材料，具有良好的可加工性和增强的性能（更高的热稳定性和机械强度，更高的玻璃化转变温度（T _g和降低的热膨胀）已被科学家和工程师长期探索。本研究表明了一种制造高性能聚合物的新方法，例如聚芳基酰胺（传统的聚芳基酰胺由于热分解前缺乏粘性流动温度而无法通过熔融加工进行加工），并且通过便捷的两步法即可获得出色的加工性能。工艺，即低温熔融加工和随后的原位热固化。通过设计含BCB的前体的结构，我们可以很好地控制熔点和固化温度，从而调节聚合物的熔融加工温度和固化温度。在我们的实验中，前驱物熔点与聚合温度之间的温差可能超过200°C，提供宽阔的处理范围和长的存储寿命。此外，这些前体在有机溶剂中也具有极好的溶解性，这使它们具有固溶或熔融加工的可能性，如代表性的前体DODA-BCB所示。所得的聚合物树脂膜显示出良好的热稳定性（T _d，5％ > 410°C），高玻璃化转变温度（T _g  > 240°C）和良好的机械强度（储能模量> 1.8 GPa）。对薄膜的热膨胀行为的进一步研究揭示了p-3,4'-ODA-BCB的热收缩特性，已使用DFT计算，VT-FTIR和TMA详细讨论了该机理。