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    双酚A-苯胺型苯并噁嗪的连续流动合成及其性能

    Continuous-Flow Synthesis and Its Properties of Bisphenol A-Aniline Benzoxazine

    • 摘要: 传统间歇合成体系传质传热能力有限,制备双酚A-苯胺型苯并噁嗪单体(BA-a)副反应多,单体闭环率(Ring-closed ratio, η)提升困难。本文构建了连续流动微反应体系,实现了单体闭环率的可控调节。在反应温度120 ℃、停留时间15 min的优化工况下,产物收率为62.3%,η达96%,综合指标优于传统间歇式方法(78 ℃,反应5 h,收率为55.1%,η为94%)。机理分析表明,较低温度或较短停留时间会导致原料转化不完全,而温度超过130 ℃、停留时间大于20 min时,噁嗪环易发生开环副反应。通过温度与停留时间的协同调控,可在实现高效转化的同时有效抑制副反应。酚羟基的自催化效应使η为91%的样品在100~120 ℃范围内的固化动力学速率加快。伴随η的升高,材料的介电常数与介电损耗持续下降,最低分别达2.92和0.0128。在质量分数为3.5% 的NaCl溶液中浸泡15d后,高闭环率(η=96%)样品的阻抗依旧保持在400 MΩ·cm2左右,表现出良好的介电特性与耐腐蚀能力。

       

      Abstract: The conventional batch synthesis system suffers from limited mass and heat transfer efficiency, leading to multiple side reactions during the preparation of bisphenol A-aniline-based benzoxazine monomer (BA-a) and making it difficult to improve the ring-closed ratio (η). To address this issue, a continuous-flow microreactor system was constructed, enabling controllable regulation of η. Under the optimized conditions of 120 ℃ and a residence time of 15 min, a product yield of 62.3% and a ring-closed ratio of 96% were achieved, demonstrating superior overall performance compared with the traditional batch method (78 ℃, 5 h, yield of 55.1%, ring-closed ratio of 94%). Mechanistic analysis indicates that lower temperatures or shorter residence times result in incomplete conversion of reactants, whereas temperatures above 130 ℃ and residence times longer than 20 min promote ring-opening side reactions of the oxazine structure. Through the synergistic control of temperature and residence time, efficient conversion can be achieved while effectively suppressing side reactions. The self-catalytic effect of phenolic hydroxyl groups accelerates the curing kinetics of samples with a ring-closed ratio of 91% within the temperature range of 100—120 ℃. With increasing ring-closed ratio, both the dielectric constant and dielectric loss of the materials continuously decrease, reaching minimum values of 2.92 and 0.0128, respectively. After immersion in 3.5% (mass fraction) NaCl solution for 15 d, sample with the high ring-closed ratio (η=96%) still maintains an impedance of about 400 MΩ·cm2, exhibiting excellent dielectric properties and corrosion resistance.

       

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