Conceptualizing flexible papers using cellulose model surfaces and polymer particles.

Cellulose, as a naturally abundant and biocompatible material, is still gaining interest due to its high potential for functionalization. This makes cellulose a promising candidate for replacing plastics. Understanding how cellulose interacts with various additives is crucial for creating composite materials with diverse properties, as it is the case for plastics. In addition, the mechanical properties of the composite materials are assumed to be related to the mobility of the additives against the cellulose. Using a well-defined cellulose model surface (CMS), we aim to understand the adsorption and desorption of two polymeric particles (core-shell particles and microgels) to/from the cellulose surface. The nanomechanics of particles and CMS are quantified by indentation measurements with an atomic force microscope (AFM). AFM topography measurements quantified particle adsorption and desorption on the CMS, while peak force AFM measurements determined the force needed to move individual particles. Both particles and the CMS exhibited pH-dependent charge behavior, allowing a tunable interaction between them. Particle adsorption was irreversible and driven by electrostatic forces. In contrast, desorption and particle mobility forces are dominated by structural morphology. In addition, we found that an annealing procedure consisting of swelling/drying cycles significantly increased the adhesion strength of both particles. Using the data, we achieve a deeper understanding of the interaction of cellulose with polymeric particles, with the potential to advance the development of functional materials and contribute to various fields, including smart packaging, sensors, and biomedical applications.

Temperature Variation Enables the Design of Biobased Block Copolymers via One-Step Anionic Copolymerization.

A one-pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature-induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at -78 °C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (-38 °C to room temperature) leads to poly(styrene-block-myrcene) formation due to polymerization of myrcene. Well-defined BCPs featuring molar masses in the range of 44-117.2 kg mol-1 with dispersities, Ð, of 1.09-1.21, and polymyrcene volume fractions of 30-64% are accessible. Matrix assisted laser desorption ionization-time of flight mass spectrometry measurements reveal the temperature-controlled polymyrcene block formation, while both transmission electron microscopy and small-angle X-ray scattering measurements prove the presence of clearly microphase-separated, long range-ordered domains in the block copolymers. The temperature-controlled one-pot anionic block copolymerization approach may be general for other terpene-diene monomers.