Photoswitching Cationic and Radical Polymerizations: Spatiotemporal Control of Thermoset Properties.

The ability to fabricate polymeric materials with spatially controlled physical properties has been a challenge in thermoset manufacturing. To address this challenge, this work takes advantage of a photoswitchable polymerization that selectively incorporates different monomers at a growing chain by converting from cationic to radical polymerizations through modulation of the wavelength of irradiation. By regulating the dosage and wavelength of light applied to the system, the mechanical properties of the crosslinked material can be temporally and spatially tuned.

Reversible redox controlled acids for cationic ring-opening polymerization.

Advancements in externally controlled polymerization methodologies have enabled the synthesis of novel polymeric structures and architectures, and they have been pivotal to the development of new photocontrolled lithographic and 3D printing technologies. In particular, the development of externally controlled ring-opening polymerization (ROP) methodologies is of great interest, as these methods provide access to novel biocompatible and biodegradable block polymer structures. Although ROPs mediated by photoacid generators have made significant contributions to the fields of lithography and microelectronics development, these methodologies rely upon catalysts with poor stability and thus poor temporal control.

On Demand Switching of Polymerization Mechanism and Monomer Selectivity with Orthogonal Stimuli.

The development of next-generation materials is coupled with the ability to predictably and precisely synthesize polymers with well-defined structures and architectures. In this regard, the discovery of synthetic strategies that allow on demand control over monomer connectivity during polymerization would provide access to complex structures in a modular fashion and remains a grand challenge in polymer chemistry. In this Article, we report a method where monomer selectivity is controlled during the polymerization by the application of two orthogonal stimuli.

Enhancing Temporal Control and Enabling Chain-End Modification in Photoregulated Cationic Polymerizations by Using Iridium-Based Catalysts.

Gaining temporal control over chain growth is a key challenge in the enhancement of controlled living polymerizations. Though research on photocontrolled polymerizations is still in its infancy, it has already proven useful in the development of previously inaccessible materials. Photocontrol has now been extended to cationic polymerizations using 2,4,6-triarylpyrylium salts as photocatalysts.

Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers.

The mechanism of the recently reported photocontrolled cationic polymerization of vinyl ethers was investigated using a variety of catalysts and chain-transfer agents (CTAs) as well as diverse spectroscopic and electrochemical analytical techniques. Our study revealed a complex activation step characterized by one-electron oxidation of the CTA. This oxidation is followed by mesolytic cleavage of the resulting radical cation species, which leads to the generation of a reactive cation-this species initiates the polymerization of the vinyl ether monomer-and a dithiocarbamate radical that is likely in equilibrium with the corresponding thiuram disulfide dimer.