Improving the solubility of the pendant-transformable acrylamide monomer enabled progress in the isospecific radical polymerization proceeding under homogeneous conditions. The subsequent addition of alcohols to the homogeneous solution allowed efficient pendant-group transformation, leading to the library synthesis of isotactic polyacrylates ( m = 96%) bearing a wide variety of side chains. Isotactic polyacrylates bearing different substituents represent a class of polymers that has not been accessible in the history of polymer synthesis, and their physical properties were therefore of considerable interest. However, these isotactic polymers did not exhibit any notable properties compared to the corresponding atactic polymers. This finding contrasts sharply with other polymer families, where stereoregularity strongly governs the material properties. Furthermore, the transformation of the isotactic precursor polymers with two different amines under homogeneous conditions enabled the synthesis of isotactic acrylamide random copolymers, whose compositions directly reflected the feed ratios of the amines. Notably, isotactic random copolymers bearing a combination of linear alkyl side chains and hydroxy-functionalized linear alkyl chains were found to exhibit crystallinity.
Pan et al. (Tue,) studied this question.