Efficient Creation and Morphological Analysis of ABC Triblock Terpolymer Libraries

Abstract

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 welldefined ABC triblock terpolymer libraries to the polymer community while also improving sample quality and accelerating discovery.

Navigating the Expansive Landscapes of Soft Materials: A User Guide for High-Throughput Workflows

“…Fractionation strategies are also able to separate disperse polymer batches to generate a library. Chromatographic techniques including thin layer chromatography (TLC), size-exclusion chromatography (SEC), reversed-phase liquid chromatography (LC), normal-phase chromatography, and ion exchange chromatography have been used in fractionation strategies (Figure c). − Although fractionation is faster than manual synthesis, only ∼10 1 can be generated with this scheme (Figure ).…”

“…A series of polymerizations can also be run using liquid-handling robots and continuous flow reactors, available at select academic and national laboratories, such as BioPACIFIC MIP , and Argonne National Laboratory’s Polybot, a self-driving laboratory for polymer development . Flow synthesis has been used for anionic, cationic, radical, and ring-opening polymerizations, , in addition to sequence-defined oligomers .…”

“…130 Library members (∼10 2 ) can be further functionalized post-polymerization prior to screening, with examples including coupling peptides to engender functionality 130 and polyethylene glycol to imbue brush-like structures. 131 A series of polymerizations can also be run using liquidhandling robots and continuous flow reactors, available at select academic and national laboratories, such as BioPACIFIC MIP 123,132 and Argonne National Laboratory's Polybot, a selfdriving laboratory for polymer development. 133 Flow synthesis has been used for anionic, cationic, radical, and ring-opening polymerizations, 134,135 in addition to sequence-defined oligomers.…”

Reexamining the Emergence and Stability of the Square Cylinder Phase in Block Copolymers

“…[22][23][24][25][26][27][28] In particular, advanced modern synthesis techniques have facilitated the precise synthesis of more and more block copolymers with various complex architectures and compositions. [29][30][31][32][33][34] More importantly, a series of guiding principles have been established, enabling the rational design of the architectures of block copolymers for new desired selfassembly structures, including conformational or architectural asymmetry, stretched bridging block and released packing frustration. [35][36][37][38][39][40][41][42][43] The conformational and architectural asymmetries, [36] respectively originating from asymmetric segment properties (e. g., segment length b and density 1) of the repeating units in different blocks and the topology of the copolymer, can deflect the phase boundaries and can even stabilize novel spherical phases.…”

“…For block copolymers, a critical factor in controlling their self‐assembly behavior is their diverse architectures [22–28] . In particular, advanced modern synthesis techniques have facilitated the precise synthesis of more and more block copolymers with various complex architectures and compositions [29–34] . More importantly, a series of guiding principles have been established, enabling the rational design of the architectures of block copolymers for new desired self‐assembly structures, including conformational or architectural asymmetry, stretched bridging block and released packing frustration [35–43] .…”