Inverse Miniemulsion Enables the Continuous-Flow Synthesis of Controlled Ultra-High Molecular Weight Polymers.

We report the controlled synthesis of ultra-high molecular weight (UHMW) polymers (Mn ≥ 106 g/mol) via continuous flow in a tubular reactor. At high monomer conversion, UHMW polymers in homogeneous batch polymerization exhibit high viscosities that pose challenges for employing continuous flow reactors. However, under heterogeneous inverse miniemulsion (IME) conditions, UHMW polymers can be produced within the dispersed phase, while the viscosity of the heterogeneous mixture remains approximately the same as the viscosity of the continuous phase. Conducting such IME polymerizations in flow results in a faster rate of polymerization compared to batch IME polymerizations while still providing excellent control over molecular weight up to 106 g/mol. Crucial emulsion parameters, such as particle size and stability under continuous flow conditions, were examined using dynamic light scattering. A range of poly(N,N-dimethylacrylamide) and poly(4-acryloylmorpholine) polymers with molecular weights of 104-106 g/mol (D ≤ 1.31) were produced by this method using water-soluble trithiocarbonates as photoiniferters.

Photoassisted Radical Depolymerization.

Controlled radical polymerization techniques enable the synthesis of polymers with predetermined molecular weights, narrow molecular weight distributions, and controlled architectures. Moreover, these polymerization approaches have been routinely shown to result in retained end-group functionality that can be reactivated to continue polymerization. However, reactivation of these end groups under conditions that instead promote depropagation is a viable route to initiate depolymerization and potentially enable closed-loop recycling from polymer to monomer. In this report, we investigate light as a trigger for thermal depolymerization of polymers prepared by reversible-addition-fragmentation chain-transfer (RAFT) polymerization. We study the role of irradiation wavelength by targeting the n → π* and π → π* electronic transitions of the thiocarbonylthio end-groups of RAFT-generated polymers to enhance depolymerization via terminal bond homolysis. Specifically, we explore depolymerization of polymers with trithiocarbonate, dithiocarbamate, and p-substituted dithiobenzoate end groups with the purpose of increasing depolymerization efficiency with light. As the wavelength decreases from the visible range to the UV range, the rate of depolymerization is dramatically increased. This method of photoassisted depolymerization allows up to 87% depolymerization efficiency within 1 h, results that may further the advancement of recyclable materials and life-cycle circularity.

Recyclable & highly porous organo-aerogel adsorbents from biowaste for organic contaminants' removal.

Selective aerogel has become an attractive adsorbent for removing oil and organic contaminants due to its low density and excellent adsorption capacity. However, aerogels usually use non-sustainable or expensive nanomaterials and require complicated fabrication processes. Herein, using low-cost lignin reclaimed from the biorefinery waste stream as the starting material, we fabricated a highly porous, mechanically strong, and stable aerogel via a simple and one-step method under mild conditions. This aerogel exhibits a controllable micropore structure and achieves quick and efficient adsorption for oil (435% g/g), as well as toxic solvents such as THF (365% g/g). The selective and stable adsorbent can be reused multiple times and the oil adsorption capacity after 5 cycles remained at 89%. This highly efficient, mechanically strong, stable, and regenerable aerogel is a potential candidate for multiple applications such as cleaning up organic contaminants, oil remediation, and oil/water separation. Meanwhile, it also employs a "waste-treat-waste" concept by adding extra value to the biorefinery process for high-efficiency circular bioeconomy.