LAUSR

2-Bromopropionyl bromide esterified cellulose nanofibrils (Br-CNFs) facilely synthesized from one-pot esterification of cellulose and in situ ultrasonication exhibited excellent N,N-dimethylformamide (DMF) dispersibility and reactivity to partially replace either chain extender or soft segment diol in the stoichiometrically optimized syntheses of polyurethanes (PUs). PUs polymerized with Br-CNF to replace either 11 mol% 1,4-butadiol chain extender OHs or 1.8 mol% polytetramethylene ether glycol OHs, i.e., 1.5 or 0.3 wt% Br-CNF in PUs, exhibited an over 3 times increased modulus, nearly 4 times higher strength, and a 50% increase in strain. In either role, the experimental modulus exceeding those predicted by the Halpin–Tsai model gave evidence of the stoichiometrically optimized covalent bonding with Br-CNF, while the improved strain was attributed to increased hydrogen-bonding interactions between Br-CNF and the soft segment. These new Br-CNFs not only offer novel synthetic strategies to incorporate nanocelluloses in polyurethanes but also maximize their reinforcing effects via their versatile polyol reactant and cross-linking roles, demonstrating promising applications in the synthesis of other polymers.