Baek Seohyun, Lee Juhyen, Kim Hyunwoo, Cha Inhwan, Song Changsik
Department of Chemistry, Sungkyunkwan University, Suwon 16419, Korea.
Polymers (Basel). 2021 Dec 14;13(24):4381. doi: 10.3390/polym13244381.
Due to growing environmental issues, research on carbon dioxide (CO) use is widely conducted and efforts are being made to produce useful materials from biomass-derived resources. However, polymer materials developed by a combined strategy (i.e., both CO-immobilized and biomass-derived) are rare. In this study, we synthesized biomass-derived poly(carbonate-co-urethane) (PCU) networks using CO-immobilized furan carbonate diols (FCDs) via an ecofriendly method. The synthesis of FCDs was performed by directly introducing CO into a biomass-derived 2,5-bis(hydroxymethyl)furan. Using mechanochemical synthesis (ball-milling), the PCU networks were effortlessly prepared from FCDs, erythritol, and diisocyanate, which were then hot-pressed into films. The thermal and thermomechanical properties of the PCU networks were thoroughly characterized by thermogravimetric analysis, differential scanning calorimetry, dynamic (thermal) mechanical analysis, and using a rheometer. The self-healing and recyclable properties of the PCU films were successfully demonstrated using dynamic covalent bonds. Interestingly, transcarbamoylation (urethane exchange) occurred preferentially as opposed to transcarbonation (carbonate exchange). We believe our approach presents an efficient means for producing sustainable polyurethane copolymers using biomass-derived and CO-immobilized diols.
由于环境问题日益严重，对二氧化碳（CO）利用的研究广泛开展，人们正在努力从生物质衍生资源中生产有用材料。然而，通过联合策略（即同时固定CO和生物质衍生）开发的聚合物材料却很少见。在本研究中，我们通过一种环保方法，使用固定CO的呋喃碳酸二醇（FCDs）合成了生物质衍生的聚（碳酸酯-共-聚氨酯）（PCU）网络。FCDs的合成是通过将CO直接引入生物质衍生的2,5-双（羟甲基）呋喃中进行的。利用机械化学合成（球磨），轻松地由FCDs、赤藓糖醇和二异氰酸酯制备了PCU网络，然后将其热压成膜。通过热重分析、差示扫描量热法、动态（热）力学分析以及使用流变仪对PCU网络的热性能和热机械性能进行了全面表征。利用动态共价键成功证明了PCU薄膜的自修复和可回收性能。有趣的是，与碳酸酯交换（转碳酸化）相反，优先发生了氨基甲酰基转移（氨基甲酸酯交换）。我们相信我们的方法为使用生物质衍生和固定CO的二醇生产可持续聚氨酯共聚物提供了一种有效手段。
