Synthesis of bio-polyol-functionalized nanocrystalline celluloses as reactive/reinforcing components in bio-based polyurethane foams by homogeneous environment modification.

Nanocrystalline Cellulose (NCC or CNC) is widely used as a filler in polymer composites due to its high specific strength, tensile modulus, aspect ratio, and sustainability. However, CNC hydrophilicity complicates its dispersion in hydrophobic polymeric matrices giving rise to aggregate structures and thus compromising its reinforcing action. CNC functionalization in a homogeneous environment, through silanization with trichloro(butyl)silane as a coupling agent and subsequent grafting with bio-based polyols, is herein investigated aiming to enhance CNC dispersibility improving the filler-matrix interaction between the hydrophobic PU and hydrophilic CNC. The modified CNCs (m_Ci) have been studied by XRD, SEM, and TGA analyses. The TGA results show that the amount of grafted polyol is strongly influenced by both its molar mass and OH number and the maximum amount of grafted polyol reaches up to 0.32 mmol per grams of functionalized CNC, within the explored conditions. The effect of different concentrations (1-3 wt%) of m_Ci on the physical, morphological, and mechanical properties of the resulting bio-based composite polyurethane foams is evaluated. Composite PU foams present compressive modulus up to 4.81 MPa and strength up to 255 kPa more than five times higher than those reinforced with unmodified CNC or with modified CNC in heterogeneous chemical environment. The improvement of mechanical properties of the examined PU foams, as a consequence of the incorporation of bio-polyols modified CNCs where polyol's OH groups interact with polyurethane precursors, could further broaden the use of these materials in building applications.