This is the first proof of concept of generating hydrophobic nanocelluloses by facile one-pot solventless telomerization using butadiene sulfone (BDS) to serve the dual functions of 1,3butadiene (BD) reagent and reaction medium. Optimal telomerization of BD at 6 equiv of 2,7-octadienyl ether (ODE) to amorphous cellulose anhydroglucose (AGU) at 110 °C, or 6ODE110, and then disintegration by shear force yielded ca. 27−41% hydrophobic DMSO, THF, and CHCl 3 dispersible nanocelluloses in 3.7, 6.3, and 4.4 nm thickness, respectively. The surface ODE group was evidenced in methylene peaks at 2800−2980 cm −1 and CC at 1640−1704 cm −1 by FTIR and in both cis and trans C2−C3 double-bond conformations at 700 and 956 cm −1 , respectively, by FTIR-ATR. Solution-state 1 H NMR elucidated the ODE structure (d 6 -DMSO; δ

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One-pot syntheses and in situ ultrasonication have been optimized to generate tunable and highly hydrophobic 2,7octadienyl-ether (ODE) cellulose nanofibrils (CNFs). Using only butadiene sulfone to serve as dual reaction medium and precursor to 1,3-butadiene (1,3-BD) for telomerization with cellulose hydroxyls, the OH-to-ODE conversion significantly improved from ca. 0.7 to 1.2, 1.8, 3.1, and 4.1 mmol of ODE/g-cellulose at 103−110 °C for 1−2 h. Ultrasonication was highly effective and versatile in the direct disintegration of ODE-cellulose (ODE-cell) in nonpolar organic solvents and plant oils into ODE-CNFs as well as pretreating cellulose for improved functionalization. Mixing 2 wt % in situ ultrasonicated 1.2 mmol of ODE/g-cell improved the modulus of polybutadiene six times and the strength of poly(styrene-b-isoprene-b-styrene) three times, whereas in situ ultrasonication of 1.8 mmol/g-cell directly with linseed oil at merely 0.07 wt % created holistic biobased hydrophobic cellulose paper to resist water penetration while also significantly improving the tensile strength. This optimized telomerization and streamlined in situ ultrasonication approach has presented a sustainable synthesis and processing strategy to generate highly hydrocarboncompatible nanocelluloses previously unattainable.

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