Polymerization mechanisms articles from across Nature Portfolio

Chemical recycling of plastic enables renewed production of pristine materials, but generally comes at a high energy cost. This review focuses on light-driven approaches for chemically recycling and upcycling plastic waste, with emphasis on reduced energy consumption and selective transformations of challenging to recycle backbone structures.

Mask-free multi-photon lithography allows the straightforward fabrication of nanostructures, but high precision and good resolution can be challenging to achieve. Here, the authors report a combination of photo-inhibition and chemical quenchers for improved lithography performance.

Mechanochemistry is a promising technology to tackle current and future polymer waste streams for a sustainable future. With this review, we take into account synthetic, computational, technical, and engineering perspectives to converge trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. We highlight the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical polymer degradation approach for a circular economy.

Acrylate polymerizations catalyzed by Lewis pairs (LP) composed of B(C₆F₅)₃ and various Lewis bases were investigated using two procedures based on different monomer/catalyst addition sequences. When Lewis bases were added to B(C₆F₅)₃-activated n-butyl acrylate (nBA) (procedure 1), the polymerization proceeded quantitatively using all Lewis bases. In contrast, the type of Lewis base significantly affected the polymerization results when nBA was added to interacting LPs (procedure 2). ¹⁹F nuclear magnetic resonance analysis of the LPs indicated that weakly interacting LPs efficiently initiated the polymerizations in procedure 2.

Acid-triggered reversible addition–fragmentation chain-transfer polymerizations, in the absence of conventional initiating species and in the dark, are reported to prepare polymers with low dispersity and high end-group fidelity. The protonation of monomers catalyses both the initiation and propagation steps and can also be applied to free radical polymerizations.

Communications Chemistry is pleased to introduce a Collection of articles focused on organomediated polymerization. Here, the Guest Editors highlight the themes within and look towards the future of this research field.

Acid triggers the formation of radicals by Flory autoinitiation of acrylic monomers and enhances polymerization rates.

Linear polyethylene and isotactic polypropylene, the two largest-volume polymers on the market, were invented in the 1950s thanks to diverse mixes of serendipity, intuition and talent. After 70 years, a thoughtful revisitation of those ground-breaking discoveries can still be revealing and inspirational.

A strategy to synthesize well-defined main-chain fluoropolymers from gaseous fluoroalkenes under ambient conditions is developed. This general approach allows for the facile tailoring of the sequence and topology of fluoropolymers comprising various comonomers.

Inverse vulcanization uses high temperatures to form sulfur-rich polymers. Now, using a photoinduced method, polymerization occurs at ambient conditions enabling a broader selection of viable comonomers compared with existing routes, as well as eliminating the formation of toxic gas.

Using anion-binding interactions to tackle challenging polymerizations is an ambitious goal and in its infancy. Seleno-cyclodiphosph(v)azanes are demonstrated to exert anion-binding interactions to precisely control the equilibrium between a dormant covalent precursor and active cationic species under mild conditions, thus enabling living cationic polymerization.