Design of melt-recyclable poly(ε-caprolactone)-based supramolecular shape-memory nanocomposites.

A novel poly(epsilon-caprolactone) (PCL) supramolecular network exhibiting shape-memory behavior was successfully constructed with pendant UPy units that are highly able to dimerize. The dynamic network was obtained by a simple and versatile strategy consisting of chain-extension reaction between α,ω-dihydroxyoligoPCL and hydroxylated UPy units in the presence of hexamethylene diisocyanate as a coupling agent and further intermolecular dimerization of the UPy along the polyurethane backbone. 1H NMR analyses confirmed the dynamic features of the system, and DMTA in tensile mode was investigated to assess the SMP properties. Recyclability was also assessed by taking advantage of these supramolecular networks. Further addition of cellulose nanocrystals into the polymer network enabled adjustment of the extent of the net-points and therefore the SMP features. As confirmed by dispersion tests in solution and SEM observations, these bio-based nanofillers were homogeneously distributed in the network via supramolecular interaction between the hydroxyl groups present on their surface and UPy moieties along the polyurethane backbone. Thus, the here developed nanomaterials might reveal applicability in areas where a combination of SMP and biocompatibility is needed.

Preparation of Cellulose Nanocrystal-Reinforced Poly(lactic acid) Nanocomposites through Noncovalent Modification with PLLA-Based Surfactants.

Cellulose nanocrystal (CNC)-reinforced poly(lactic acid) (PLA) nanocomposites were prepared by twin-screw extrusion followed by injection-molding using a masterbatch approach. Noncovalent modification of CNCs was performed with two different poly(l-lactide) (PLLA)-based surfactants to improve the filler/matrix compatibility. They both have a PLLA block that is expected to improve the compatibility with the PLA matrix and differ by the polar head. It consists of either a poly(ethylene glycol) (PEG) block (PEG-b-PLLA) or an imidazolium group (Im-PLLA), that is able to interact with the surface of the CNCs. The morphological, structural, thermal, rheological, and mechanical properties of the nanocomposites were investigated. The different modes of interaction of the polar head of the surfactant lead to different properties. However, the global decrease in the molecular weight of PLA, induced by the short PLLA blocks from the surfactants and the possible degradation during melt processing, results in a plasticization effect and impacts the crystallization of the matrix.