title: Site-Selective Modification of Cellulose Nanocrystals with Isophorone Diisocyanate and Formation of Polyurethane-CNC Composites.
abstract: The unequal reactivity of the two isocyanate groups in an isophorone diisocyante (IPDI) monomer was exploited to yield modified cellulose nanocrystals (CNCs) with both urethane and isocyanate functionality. The chemical functionality of the modified CNCs was verified with ATR-FTIR analysis and elemental analysis. The selectivity for the secondary isocyanate group using dibutyl tin dilaurate (DBTDL) as the reaction catalyst was confirmed with (13)C NMR. The modified CNCs showed improvements in the onset of thermal degradation by 35 °C compared to the unmodified CNCs. Polyurethane composites based on IPDI and a trifunctional polyether alcohol were synthesized using unmodified (um-CNC) and modified CNCs (m-CNC). The degree of nanoparticle dispersion was qualitatively assessed with polarized optical microscopy. It was found that the modification step facilitated superior nanoparticle dispersion compared to the um-CNCs, which resulted in increases in the tensile strength and work of fracture of over 200% compared to the neat matrix without degradation of elongation at break.
authors.forename: Natalie M
authors.initials: NM
authors.lastname: Girouard
authors.affiliation: National Institute of Standards and Technology , Gaithersburg, Maryland, United States.
authors.forename: Shanhong
authors.initials: S
authors.lastname: Xu
authors.affiliation: Forest Products Laboratory, U.S. Forest Service , Madison, Wisconsin, United States.
authors.forename: Gregory T
authors.initials: GT
authors.lastname: Schueneman
authors.forename: Meisha L
authors.initials: ML
authors.lastname: Shofner
authors.forename: J Carson
authors.initials: JC
authors.lastname: Meredith
keywords: cellulose nanocrystal; dispersion; isocyanate chemistry; mechanical properties; nanoparticle modification; polymer nanocomposite; polyurethane; thermal stability