低温热RAFT脱聚:Z组替代剂对分子量控制和产量的影响
Nethmi De Alwis Watuthanthrige1, Anastasiia Moskalenko1, Asja A Kroeger2
1Laboratory of Polymeric Materials, Department of Materials, ETH Zurich Vladimir Prelog Weg 5 8093 Zurich Switzerland athina.anastasaki@mat.ethz.ch.
Chemical science
|January 30, 2025
概括
研究人员通过可逆添加-碎片化链转移 (RAFT) 聚合优化了聚合甲酸盐的低温化学回收. 在RAFT剂上的电子捐赠组显著提高了单体回收,使得高效的聚合物脱聚合成为可能.
科学领域:
- 聚合物化学 聚合物化学
- 可持续化学 可持续化学
- 化学回收利用 化学回收利用
背景情况:
- 像ATRP和RAFT这样的受控激素聚合方法能够有效地回收聚合甲酸盐的化学物质.
- 目前的热脱聚合策略往往需要高温 (120-170°C),从而在较温和的条件下实现较慢的速度和适度的产量.
- 优化脱聚合条件对于可持续的聚合物回收至关重要.
研究的目的:
- 为了研究Z组替代对低温聚合甲基酸脱聚合的dithiobenzoate RAFT剂的影响.
- 为了提高单体回收率和控制降低温度下的脱聚合率.
- 了解管理RAFT介导的聚合物化学回收的结构-活性关系.
主要方法:
- 合成各种dithiobenzoate RAFT剂与不同的Z组替代剂 (电子捐赠和电子提取).
- 在90°C下使用这些RAFT剂去聚合聚合甲酸盐.
- 使用像1H NMR光谱学这样的技术分析单体转化.
- 分子重量测定以评估脱聚合控制.
- 密度函数理论 (DFT) 计算以阐明反应机制.
主要成果:
- 电子捐赠的Z组 (例如,甲基,三级丁基) 在90°C时显著增加了单体回收率,达到75%的回收率,比取电子的组提高了四倍.
- 提取电子的Z组 (例如,三甲基,三甲氧) 导致转换率较低 (18%),但对分子量减少提供了更好的控制.
- DFT的计算证实了与电子捐赠Z组的加速键分裂.
结论:
- 在RAFT剂中选择Z组对于调整低温聚合甲酸脱聚合物的效率和控制至关重要.
- 电子捐赠组促进更高的单体回收,而电子吸收组可以更好地控制脱聚合过程.
- 这项研究为设计有效的RAFT剂提供了一条途径,以在较低温度下有效和受控地回收聚合甲酸的化学物质.
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