Fully Atom-Efficient\nSolvent-Mediated Biopolymer Manufacturing:\nA Base Case Illustrated with Macromolecular Surfactants Tailored to\nStable Polymer–Water Interfaces

This work introduces a novel 1-pot, 0-waste, 0-VOC methodology\nfor synthesizing polymeric surfactants using acrylated epoxidized\nsoybean oil and acrylated glycerol as primary monomers. These macromolecular\nsurfactants are synthesized via reversible addition–fragmentation\nchain transfer (RAFT) polymerization, allowing for tunable hydrophilic–lipophilic\nbalance (HLB) and ionic properties. We characterize the copolymers’\nchemical composition and surface–active properties, and evaluate\ntheir effectiveness in forming and stabilizing emulsions of semiepoxidized\nsoybean oil and poly(acrylated epoxidized high oleic soybean oil).\nComprehensive analyses, including gel permeation chromatography, nuclear\nmagnetic resonance spectroscopy, dynamic light scattering, particle\nsize distribution, zeta potential, and critical micelle concentration,\nprovide detailed insights into the copolymers and the emulsions they\nform. The results demonstrate that the RAFT-polymerized surfactants\noffer long-lasting stability and effectively disperse both common\noil-in-water emulsions and highly viscous and hydrophobic polymer\nlatexes. These surfactants outperform traditional small molecule surfactants\nby reducing particle size and preventing phase separation, even over\nextended storage periods. Stable polymer–water interfaces are\nachieved through HLB control, tailored by monomer composition, and\nthe final product requires no additional purification since polymerization\noccurs in liquid surfactants. While small molecules contribute to\nrapid micelle formation, the polymeric components enhance long-term\nstability through steric repulsion and slower dynamics. This method\nenables even the emulsification of polymers with submicron particle\nsize, which ordinarily requires emulsion polymerization. Integrating\nbiobased polymeric surfactants with advanced polymer processing techniques\nopens new possibilities for transforming highly hydrophobic polymers\ninto latexes, facilitating downstream applications. This innovation\nenhances the environmental sustainability of surfactant production\nand broadens the potential for polymer emulsification technologies.\nAdditionally, the integrated solution-processing approach demonstrated\nhere can be applied to other emerging polymers, where judiciously\nselected nonvolatile solvents facilitate the polymerization and play\na role in the final application.