Synthesis and Self-Assembly of Discrete Dimethylsiloxane–Lactic Acid Diblock Co-oligomers: The Dononacontamer and Its Shorter Homologues

Most of the theoretical and computational descriptions of the phase behavior of block copolymers describe the chain ensembles of perfect and uniform polymers. In contrast, experimental studies on block copolymers always employ materials with disperse molecular makeup. Although most polymers are so-called monodisperse, they still have a molecular weight dispersity. Here, we describe the synthesis and properties of a series of discrete length diblock co-oligomers, based on oligo-dimethylsiloxane (<i>o</i>DMS) and oligo-lactic acid (<i>o</i>LA), diblock co-oligomers with highly noncompatible blocks. By utilizing an iterative synthetic protocol, co-oligomers with molar masses up to 6901 Da, ultralow molar mass dispersities (<i><i>Đ</i></i> ≤ 1.00002), and unique control over the co-oligomer composition are synthesized and characterized. This specific block co-oligomer required the development of a new divergent strategy for the <i>o</i>DMS structures by which both bis- and monosubstituted <i>o</i>DMS derivatives up to 59 Si-atoms became available. The incompatibility of the two blocks makes the final coupling more demanding the longer the blocks become. These optimized synthetic procedures granted access to multigram quantities of most of the block co-oligomers, useful to study the lower limits of block copolymer phase segregation in detail. Cylindrical, gyroid, and lamellar nanostructures, as revealed by DSC, SAXS, and AFM, were generated. The small oligomeric size of the block co-oligomers resulted in exceptionally small feature sizes (down to 3.4 nm) and long-range organization