Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate).

The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for the introduction of backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues for the selective deconstruction of multiple classes of vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize with methacrylates to an appreciable extent to enable polymer deconstruction. Here, we overcome this challenge through the design of a new class of benzyl-functionalized thionolactones (bDOTs). Guided by detailed mechanistic analyses, we find that the introduction of radical-stabilizing substituents to bDOTs enables markedly increased and tunable copolymerization reactivity with methyl methacrylate (MMA). Through iterative optimizations of the molecular structure, a specific bDOT, F-p-CF3PhDOT, is discovered to copolymerize efficiently with MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, Mn > 120 kDa) with low percentages of F-p-CF3PhDOT (1.8 and 3.8 mol%) are prepared using industrially relevant bulk free radical copolymerization conditions. The thermomechanical properties of dPMMA are similar to PMMA; however, the former is shown to degrade into low molar mass fragments (<6.5 kDa) under mild aminolysis conditions. This work presents the first example of a radical ring-opening CC capable of nearly random copolymerization with MMA without the possibility of cross-linking and provides a workflow for the mechanism-guided design of deconstructable copolymers in the future.

Thermally Robust yet Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)-Like Materials Based on Si-O Bonds.

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl- and olefin-related functional groups. Bifunctional silyl ethers (BSEs; SiR2 (OR'2 )) could expand the functional scope of PE mimics as they possess strong Si-O bonds and facile chemical tunability. Here, we report BSE-containing high-density polyethylene (HDPE)-like materials synthesized through a one-pot catalytic ring-opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si-substituents, providing handles to control thermomechanical properties. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid-catalyzed Si-O bond exchange with 1-propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain-growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step-growth Si-O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.

Orthogonally deconstructable and depolymerizable polysilylethers via entropy-driven ring-opening metathesis polymerization.

The synthesis of novel polysilylethers via entropy-driven ring-opening metathesis polymerization (ED-ROMP) of cyclic bifunctional silyl ether-based monomers is reported. These polymers display good thermal stability and ultra-low Tg (-88 °C). Moreover, they are rapidly deconstructable via the cleavage of the silicon-oxygen linkages with acid or fluoride triggers, and they were partially depolymerizable by the addition of exogenous metathesis catalyst. Analysis of the deconstructed polymer products provided insight into the polymer microstructure, showing that the ED-ROMP process was regiorandom. Altogether, this work offers a new class of deconstructable polymers with a range of potential applications.

Cleavable Comonomers for Chemically Recyclable Polystyrene: A General Approach to Vinyl Polymer Circularity.

Many common polymers, especially vinyl polymers, are inherently difficult to chemically recycle and are environmentally persistent. The introduction of low levels of cleavable comonomer additives into existing vinyl polymerization processes could facilitate the production of chemically deconstructable and recyclable variants with otherwise equivalent properties. Here, we report thionolactones that serve as cleavable comonomer additives for the chemical deconstruction and recycling of vinyl polymers prepared through free radical polymerization, using polystyrene (PS) as a model example. Deconstructable PS of different molar masses (∼20-300 kDa) bearing varied amounts of statistically incorporated thioester backbone linkages (2.5-55 mol %) can be selectively depolymerized to yield well-defined thiol-terminated fragments (<10 kDa) that are suitable for oxidative repolymerization to generate recycled PS of nearly identical molar mass to the parent material, in good yields (80-95%). A theoretical model is provided to generalize this molar mass memory effect. Notably, the thermomechanical properties of deconstructable PS bearing 2.5 mol % of cleavable linkages and its recycled product are similar to those of virgin PS. The additives were also shown to be effective for deconstruction of a cross-linked styrenic copolymer and deconstruction and repolymerization of a polyacrylate, suggesting that cleavable comonomers may offer a general approach toward circularity of many vinyl (co)polymers.

Synthesis of C6-Substituted Purine Nucleoside Analogues via Late-Stage Photoredox/Nickel Dual Catalytic Cross-Coupling.

Nucleoside analogues have been and continue to be extremely important compounds in drug discovery. Despite the significant effort dedicated to their synthesis, medicinal chemistry campaigns around these structures are often hampered by synthetic challenges. We describe a strategy for the functionalization of purine nucleosides via photoredox and nickel-catalyzed sp2-sp3 cross-coupling. The conditions described herein allow for coupling of unprotected nucleosides with readily available alkyl bromides, providing opportunities for their application to parallel medicinal chemistry.

Cooperative Effects between Hydrophilic Pores and Solvents: Catalytic Consequences of Hydrogen Bonding on Alkene Epoxidation in Zeolites.

Hydrophobic voids within titanium silicates have long been considered necessary to achieve high rates and selectivities for alkene epoxidations with H2O2. The catalytic consequences of silanol groups and their stabilization of hydrogen-bonded networks of water (H2O), however, have not been demonstrated in ways that lead to a clear understanding of their importance. We compare turnover rates for 1-octene epoxidation and H2O2 decomposition over a series of Ti-substituted zeolite *BEA (Ti-BEA) that encompasses a wide range of densities of silanol nests ((SiOH)4). The most hydrophilic Ti-BEA gives epoxidation turnover rates that are 100 times larger than those in defect-free Ti-BEA, yet rates of H2O2 decomposition are similar for all (SiOH)4 densities. These differences cause the most hydrophilic Ti-BEA to also give the highest selectivities, which defies conventional wisdom. Spectroscopic, thermodynamic, and kinetic evidence indicate that these catalytic differences are not due to changes in the electronic affinity of the active site, the electronic structure of Ti-OOH intermediates, or the mechanism for epoxidation. Comparisons of apparent activation enthalpies and entropies show that differences in epoxidation rates and selectivities reflect favorable entropy gains produced when epoxidation transition states disrupt hydrogen-bonded H2O clusters anchored to (SiOH)4 near active sites. Transition states for H2O2 decomposition hydrogen bond with H2O in ways similar to Ti-OOH reactive species, such that decomposition becomes insensitive to the presence of (SiOH)4. Collectively, these findings clarify how molecular interactions between reactive species, hydrogen-bonded solvent networks, and polar surfaces can influence rates and selectivities for epoxidation (and other reactions) in zeolite catalysts.