Copolyampholytes Produced from RAFT Polymerization of Protic Ionic Liquids,Macromolecules

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Copolyampholytes Produced from RAFT Polymerization of Protic Ionic Liquids
Macromolecules ( IF 5.1 ) Pub Date : 2017-11-10 00:00:00 , DOI: 10.1021/acs.macromol.7b01768
Céline C. J. Fouillet _{1,

2} , Tamar L. Greaves ₁ , John F. Quinn ₂ , Thomas P. Davis _{2,

3} , Jozef Adamcik ₄ , Marc-Antoine Sani ₅ , Frances Separovic ₅ , Calum J. Drummond ₁ , Raffaele Mezzenga ₄

Affiliation

Polyampholytic copolymers have been synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization of protic ionic liquid monomers. The monomers were prepared by acid–base proton exchange between acid and basic precursor conjugates, each containing one or more vinyl pendant groups. The polymerization, which was carried out without additional solvents present, led to high molecular weight glassy polymers, which were stable in the form of bulk viscous liquid ionic complexes. Various polyampholytes belonging to both linear and cross-linked families were prepared by judiciously varying the molecular structure of the acid precursor. Furthermore, by using solid-state NMR, the molecular arrangement of the polymeric backbone was identified, highlighting the presence of copolymers with both random and alternating copolymer chains which in the latter case involves a regularly alternating acid monomer, whereas the base occurs as a random sequence with the average and most probable number of monomers dictated by the stoichiometry used. The structural and mechanical properties of the resulting copolyampholytes were characterized by atomic force microscopy, peak-force quantitative nanomechanical analysis, differential scanning calorimetry, and small-angle X-ray scattering. These showed that the final polymers were essentially glassy and amorphous, with weak compositional fluctuations of the order of a few monomers and Young moduli in the range 1–3 GPa.

中文翻译：

质子离子液体的RAFT聚合产生的共聚两性电解质

聚两性共聚物是通过质子离子液体单体的可逆加成-断裂链转移（RAFT）聚合而合成的。单体是通过酸与碱性前体共轭物之间的酸碱质子交换而制备的，每种共轭物均包含一个或多个乙烯基侧基。在不存在额外溶剂的情况下进行的聚合反应产生了高分子量玻璃状聚合物，其以本体粘性液体离子络合物的形式稳定。通过明智地改变酸前体的分子结构，可以制备属于直链和交联家族的各种多两性电解质。此外，通过使用固态NMR，可以确定聚合物主链的分子排列，强调了存在具有无规和交替共聚物链的共聚物，在后一种情况下，该共聚物涉及规则的交替酸单体，而碱以无规序列的形式出现，其单体的平均和最可能数由所用化学计量学决定。通过原子力显微镜，峰力定量纳米力学分析，差示扫描量热法和小角X射线散射对所得共聚两性电解质的结构和力学性能进行了表征。这些结果表明，最终的聚合物基本上是玻璃态和无定形的，一些单体的数量级波动较小，杨氏模量在1-3 GPa范围内。而碱基以随机序列的形式出现，其平均和最可能的单体数量由所用化学计量法决定。通过原子力显微镜，峰力定量纳米力学分析，差示扫描量热法和小角X射线散射对所得共聚两性电解质的结构和力学性能进行了表征。这些结果表明，最终的聚合物基本上是玻璃态和无定形的，一些单体的数量级波动较小，杨氏模量在1-3 GPa范围内。而碱基以随机序列的形式出现，其平均和最可能的单体数量由所用化学计量法决定。通过原子力显微镜，峰力定量纳米力学分析，差示扫描量热法和小角X射线散射对所得共聚两性电解质的结构和力学性能进行了表征。这些结果表明，最终的聚合物基本上是玻璃态和无定形的，一些单体的数量级波动较小，杨氏模量在1-3 GPa范围内。和小角度X射线散射。这些结果表明，最终的聚合物基本上是玻璃态和无定形的，一些单体的数量级波动较小，杨氏模量在1-3 GPa范围内。和小角度X射线散射。这些结果表明，最终的聚合物基本上是玻璃态和无定形的，一些单体的数量级波动较小，杨氏模量在1-3 GPa范围内。

更新日期：2017-11-10

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