Synthesis of Degradable Polysulfamides via Sulfur(VI) Fluoride Exchange Click Polymerization of AB-Type Monomers.
Synthesis of Degradable Polysulfamides via Sulfur(VI) Fluoride Exchange Click Polymerization of AB-Type Monomers.
复制标题
ab型单体硫（VI）氟交换点击聚合合成可降解聚磺胺。
DOI：
10.1021/acspolymersau.2c00060
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发表时间：
2023-06-14
期刊：
影响因子：
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通讯作者：
Michaudel, Quentin
中科院分区：
文献类型：
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作者：
Wu, Jiun Wei;Kulow, Ryan W;Redding, McKenna J;Fine, Alexander J;Grayson, Scott M;Michaudel, Quentin
聚磺酰胺是聚脲的−SO2-类似物，形成了一个有趣的含有氢键供体和受体基团的聚合物家族。然而，与聚脲不同，它们的物理性质大多是未知的，因为缺乏获得这种聚合物的合成方法。在此，我们报告了一种方便的合成AB单体的合成聚磺酰胺通过硫（VI）氟化物交换（SuFEx）点击聚合。在优化的逐步增长的过程中，各种聚磺酰胺被分离和表征。SuFEx聚合的多功能性允许通过引入脂肪族或芳香族胺来调节主链的结构。虽然所有合成的聚合物通过热重分析呈现高的热稳定性，但通过差示扫描量热法和粉末X-射线衍射显示玻璃化转变温度和结晶度与重复磺酰胺单元之间的主链结构高度相关。通过基质辅助激光解吸/电离飞行时间质谱和X-射线晶体学的仔细分析也揭示了一个AB单体聚合过程中形成的大环低聚物。最后，开发了两种方案，以有效地降解所有合成的聚磺酰胺，通过化学回收的聚合物衍生自芳族胺或氧化升级循环的那些基于脂肪族胺。
Polysulfamides are the −SO2– analogues of polyureas and form an intriguing family of polymers containing hydrogen-bond donor and acceptor groups. However, unlike polyureas, their physical properties are mostly unknown because of the scarcity of synthetic methods to access such polymers. Herein, we report an expedient synthesis of AB monomers for the synthesis of polysulfamides via Sulfur(VI) Fluoride Exchange (SuFEx) click polymerization. Upon optimization of the step-growth process, a variety of polysulfamides were isolated and characterized. The versatility of the SuFEx polymerization allowed structural modulation of the main chain through the incorporation of aliphatic or aromatic amines. While all synthesized polymers presented high thermal stability via thermogravimetric analysis, the glass-transition temperature and crystallinity were shown to be highly tied to the structure of the backbone between repeating sulfamide units through differential scanning calorimetry and powder X-ray diffraction. Careful analysis via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and X-ray crystallography also revealed the formation of macrocyclic oligomers during the polymerization of one AB monomer. Finally, two protocols were developed to efficiently degrade all synthesized polysulfamides through either chemical recycling for polymers derived from aromatic amines or oxidative upcycling for those based on aliphatic amines.