Synthesis of Tailored Segmented Polyurethanes Utilizing Continuous-Flow Reactors and Real-Time Process Monitoring

Abstract

Conducting polymerizations under continuous-flow conditions affords distinct advantages over batch experimentation and has increasingly been employed by the research community for chain-growth polymerizations to accelerate material discovery and to finely tune material properties. This work now expands on the reported advances by demonstrating the utility of continuous flow for polyaddition reactions of polyurethanes (PUs). Various reactor configurations enable the on-demand organocatalytic one-step synthesis of linear PUs with tailored soft-to-hard segment ratios in 3–5 min at room temperature. In-line analytics is implemented for real-time process monitoring and to develop process control mechanisms, increasing the control over monomer conversion and material quality and minimizing batch-to-batch variations. The reported strategies thus provide a guideline for the straightforward preparation of libraries of commercially relevant PU materials.

Self-healable dynamic poly(urea-urethane) gel electrolyte for lithium batteries

“…29,31 Their adaptable synthesis allows ad hoc material properties tailored to their nal application. 32,33 Besides, most of the starting reactants (common polyols, isocyanates and small molecular weight diols/diamines) are well known and have been employed industrially for several decades; polyurethanes still offer an open door for the introduction of more sophisticated compounds that could play a key role in advanced energy storage applications. As an example, single-ion conducting polyurethane electrolytes were studied by Porcarelli et al, 34 while a review article on polyurethane-based polymer electrolytes for LIBs has recently summarized the main advantages.…”

Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐Ð Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control

“…[ 29–31 ] The alternative used so far to overcome these secondary reactions is to conduct the polymerization at low temperatures (≤60 °C) with anhydrous aprotic solvents. [ 10,23,26,32–37 ] However, this strategy increases the environmental impact as well as the labor required for PU synthesis for advanced applications.…”

“…Polyurethanes (PUs) form one of the most widely produced classes of polymers due to their wide variety of compositions, and DOI: 10.1002/macp.202200129 consequently properties and applications. [1][2][3][4][5][6][7][8][9][10][11] The growing appeal of sustainable materials and novel polymeric materials for biomedical applications increased the interest in polyurethane synthesis in the past 10 years, specially PEG-based PUs. [12][13][14][15][16][17][18][19][20][21][22][23] However, the control of the molar mass and molar mass dispersity (Ð ≤ 1.5), as well as of the architecture of PU, is still challenging.…”

“…[29][30][31] The alternative used so far to overcome these secondary reactions is to conduct the polymerization at low temperatures (≤60 °C) with anhydrous aprotic solvents. [10,23,26,[32][33][34][35][36][37] However, this strategy increases the environmental impact as well as the labor required for PU synthesis for advanced applications. In this context, recent progress has been made in the development of a new synthetic route for polyurethanes called dynamic urea bond-mediated polymerization (DUBMP).…”

An extensible software platform for accelerating polymer discovery through informatics and artificial intelligence development

“…25 Despite these advances, there remains an unmet need for flexible and interoperable data models and polymer representation formats. This became evident in our own research while merging historical data from disparate areas of monomer synthesis, 26,27 organocatalyst development, 28 post-polymerization modification, 29 continuous-flow polymerization, [30][31][32][33] therapeutic materials, 34 polymer recycling, 35 and more, into a unified system to support AI/ML development for polymers proved to be exceedingly challenging and beyond the scope of existing data management solutions. These difficulties are not unique and serve as a microcosm for the much broader field of polymer science, given the breadth of application domains, molecular length scales, experiment types, and properties.…”