Sustainably producing plastics with performance properties across a variety of materials chemistries is a major challenge—especially considering that most performance materials use aromatic precursors that are still difficult to source sustainably. Here we demonstrate catalyst-free, melt polymerization of dimethyl glyoxylate xylose, a stabilized carbohydrate that can be synthesized from agricultural waste with 97% atom efficiency, into amorphous polyamides with performances comparable to fossil-based semi-aromatic alternatives. Despite the presence of a carbohydrate core, these materials retain their thermomechanical properties through multiple rounds of high-shear mechanical recycling and could be chemically recycled. Techno-economic and life-cycle analyses suggest selling prices close to those of nylon 66 with a reduction of global warming potential of up to 75%. This work illustrates the versatility of a carbohydrate moiety to impart performance that can compete with that of semi-aromatic polymers across two important materials chemistries.

Functional ring‐opening polymerization (ROP) initiators can instill a wide array of chemical, physical, and biological effects into a polymeric chain. Highlighting the versatility of this “active” initiator approach, a broad range of characteristics can be achieved through the use of initiators with chemistries spanning from drugs and dyes (key in the case of drug delivery or nanoparticle applications) through to radically active monomers, polymerization transfer agents, and catalysts. The selection of a suitable “active” initiator (monomers for tandem reactions, dyes, drugs, stereo‐catalysts, etc.) can not only provide the final polymers with interesting application potential but also facilitate the implementation of ROP reactions in tandem with other polymerization techniques. Overall, this review will highlight that functionalities and properties can be effectively tuned by exploiting simple chemistry approaches, allowing readers to identify how these approaches could be of benefit to their own work in a range of applications including drug/gene delivery, amphiphilic bio/degradable carriers, drug/scent controlled release, and stereo‐controlled polymers.

RAFT dispersion polymerisation of methyl methacrylate is performed in scCO ₂ with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight.

A combined computational/experimental approach has been applied to investigate the self-crosslinking of α-pinene methacrylate via chain transfer through hydrogen abstraction.