pH-Responsive Shape Memory Poly(ethylene glycol)–Poly(ε-caprolactone)-based Polyurethane/Cellulose Nanocrystals Nanocomposite

Abstract

In this study, we developed a pH-responsive shape-memory polymer nanocomposite by blending poly­(ethylene glycol)–poly­(ε-caprolactone)-based polyurethane (PECU) with functionalized cellulose nanocrystals (CNCs). CNCs were functionalized with pyridine moieties (CNC–C₆H₄NO₂) through hydroxyl substitution of CNCs with pyridine-4-carbonyl chloride and with carboxyl groups (CNC–CO₂H) via 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated surface oxidation, respectively. At a high pH value, the CNC–C₆H₄NO₂ had attractive interactions from the hydrogen bonding between pyridine groups and hydroxyl moieties; at a low pH value, the interactions reduced or disappeared due to the protonation of pyridine groups, which are a Lewis base. The CNC–CO₂H responded to pH variation in an opposite manner. The hydrogen bonding interactions of both CNC–C₆H₄NO₂ and CNC–CO₂H can be readily disassociated by altering pH values, endowing the pH-responsiveness of CNCs. When these functionalized CNCs were added in PECU polymer matrix to form nanocomposite network which was confirmed with rheological measurements, the mechanical properties of PECU were not only obviously improved but also the pH-responsiveness of CNCs could be transferred to the nanocomposite network. The pH-sensitive CNC percolation network in polymer matrix served as the switch units of shape-memory polymers (SMPs). Furthermore, the modified CNC percolation network and polymer molecular chains also had strong hydrogen bonding interactions among hydroxyl, carboxyl, pyridine moieties, and isocyanate groups, which could be formed or destroyed through changing pH value. The shape memory function of the nanocomposite network was only dependent on the pH variation of the environment. Therefore, this pH-responsive shape-memory nancomposite could be potentially developed into a new smart polymer material