Efficient Creation and Morphological Analysis of ABC Triblock Terpolymer Libraries
Efficient Creation and Morphological Analysis of ABC Triblock Terpolymer Libraries
复制标题
DOI：
10.1021/acs.macromol.2c01480
复制
发表时间：
2022-10
期刊：
影响因子：
5.5
通讯作者：
Elizabeth A. Murphy;Yan-Qiao Chen;Kaitlin R. Albanese;Jacob R. Blankenship;Allison Abdilla;M. Bates;Cheng Zhang;Christopher M. Bates;C. Hawker
中科院分区：
文献类型：
--
作者：
Elizabeth A. Murphy;Yan-Qiao Chen;Kaitlin R. Albanese;Jacob R. Blankenship;Allison Abdilla;M. Bates;Cheng Zhang;Christopher M. Bates;C. Hawker
嵌段序列日益复杂的多嵌段共聚物（例如三嵌段三元共聚物）为制造纳米结构材料提供了独特的机会，但这种潜力受到了巨大设计空间的阻碍，这使得结构-性能关系的探索变得复杂。在这里，我们报告了一个通用的和可扩展的策略，分离母ABC和异构ACB三嵌段三元共聚物到库的分馏样品跨越广泛的组合物。使用受控聚合和自动色谱的组合，合成和分离不到10种ABC和ACB母体材料，产生了超过100种纯化的三嵌段三元共聚物。分离遵循系统的和可预测的体积分数的趋势，从吸附为基础的机制，其中富含非极性块的链首先是非极性的，其次是更极性的衍生物，产生馏分的组成和摩尔质量分散度的纯度提高。正如小角X-射线散射所证明的那样，与合成的母体材料相比，分馏显著增强了长程有序性，并允许对各种纳米级形态进行明确的鉴定。这种用户友好的分离策略显着增加了聚合物社区定义明确的ABC三嵌段聚合物库的可用性，同时还提高了样品质量并加速了发现。
Multiblock copolymers with increasingly complex block sequences─for example, triblock terpolymers─offer unique opportunities to create nanostructured materials, but this potential has been hindered by a vast design space that complicates the exploration of structure–property relationships. Here, we report a versatile and scalable strategy to separate parent ABC and isomeric ACB triblock terpolymers into libraries of fractionated samples spanning a wide range of compositions. Using a combination of controlled polymerization and automated chromatography, the synthesis and separation of less than 10 ABC and ACB parent materials gave rise to over 100 purified triblock terpolymers. Separations follow systematic and predictable trends in volume fraction resulting from an adsorption-based mechanism where chains rich in non-polar blocks elute first, followed by more polar derivatives, yielding fractions with improved purity in composition and molar-mass dispersity. As evidenced by small-angle X-ray scattering, fractionation significantly enhances long-range order compared to as-synthesized parent materials and allows for the definitive identification of various nanoscale morphologies. This user-friendly separation strategy significantly increases the availability of well-defined ABC triblock terpolymer libraries to the polymer community while also improving sample quality and accelerating discovery.