Scott Sabrina S, Zeng Yimin, Wright Taylor, Wolf Michael O, Schafer Laurel L
Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z4, Canada.
Macromol Rapid Commun. 2024 Dec;45(23):e2400444. doi: 10.1002/marc.202400444. Epub 2024 Oct 1.
Polymerization of primary amine-containing monomers is challenging because the amine inhibits polymerization catalyst activity. An alternative approach to access primary amine functionalized polymers is postpolymerization modification. To this end, the hydroaminoalkylation of vinyl-terminated polyolefins with N-(trimethylsilyl)benzylamine is used to prepare primary amine-terminated polyolefins, with the free primary amine substituent being revealed upon hydrolytic work up. These materials are spectroscopically characterized, and an investigation of thermal properties by differential scanning calorimetry and thermogravimetric analysis is completed. These results show that the primary amine substituent increases the glass transition temperature and improves thermal stability. The reactive primary amine functionality is used in the photo-oxidative dimerization of polyolefins to demonstrate how this elusive functionality can be applied in oligomer valorization.
含伯胺单体的聚合具有挑战性，因为胺会抑制聚合催化剂的活性。获得伯胺官能化聚合物的另一种方法是后聚合改性。为此，使用乙烯基封端的聚烯烃与N-（三甲基硅基）苄胺进行氢胺烷基化反应来制备伯胺封端的聚烯烃，在水解后处理时会暴露出游离的伯胺取代基。对这些材料进行了光谱表征，并通过差示扫描量热法和热重分析完成了热性能研究。这些结果表明，伯胺取代基提高了玻璃化转变温度并改善了热稳定性。活性伯胺官能团用于聚烯烃的光氧化二聚反应，以证明这种难以捉摸的官能团如何应用于低聚物增值。
