Tuning Single-Polymer Growth via Hydrogen Bonding in Conformational Entanglements

[Image: see text] Synthetic polymers have widespread applications in daily life and advanced materials applications. Making polymers efficiently and controllably is highly desired, for which modulating intramolecular and intermolecular interactions have been an effective approach. Recent real-time single-polymer growth studies uncovered nonequilibrium conformational entanglements that form stochastically under living polymerization conditions and which appear to plausibly play key roles in controlling the polymerization kinetics and dispersion. Here, using magnetic tweezers measurements, we study the real-time polymerization dynamics of single polynorbornene-based polymers in which we systematically tune the hydrogen-bonding interactions by titrating the OH content in the monomers and the formed polymers during ring opening metathesis polymerization. Using norbornenes with and without a hydroxyl group and a nonreactive monomer analogue, we show that intrachain and intermolecular hydrogen bonding compete, and both alter the microscopic properties of the nonequilibrium entanglements, leading to surprising multiphasic dependences of polymerization dynamics on the polymer’s OH content. We further formulate a simple model to rationalize quantitatively the observed multiphasic behaviors by considering the different scaling relations of intrachain and intermolecular hydrogen bonding on the OH content. These results provide insights into the interconnected roles of intra-/intermolecular interactions, polymer chain conformations, and free monomers in solution in affecting polymerization kinetics and dispersion, and point to new opportunities in manipulating polymerization reactions.