Resorcinol-Derived Vitrimers and Their Flax Fiber-Reinforced Composites Based on Fast Siloxane Exchange.

Natural fiber-reinforced composites are gaining increased interest for their significantly reduced carbon footprint compared to conventional glass or carbon fiber-based counterparts. In this study, natural fibers are used in a resorcinol-based epoxy resin that is thermally reshapable at higher temperatures (>180 °C) by using fast exchanging siloxane bonds, catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene. Stress relaxation times of only about 6 s at 220 °C can be reached. A resorcinol-based epoxy compound is selected because it can be derived from cellulose, opening ways for more sustainable and reshapable composite materials. In a last step of the research, the low viscosity vitrimer formulation (<200 mPa s) is applied to make a flax fiber-reinforced composite using an industrially relevant vacuum-assisted resin infusion process. A section of this composite is successfully reshaped, which allows for envisioning a second life for natural fiber-reinforced composites.

Fast Dynamic Siloxane Exchange Mechanism for Reshapable Vitrimer Composites.

To develop siloxane-containing vitrimers with fast dynamic characteristics, different mechanistic pathways have been investigated using a range of catalysts. In particular, one siloxane exchange pathway has been found to show a fast dynamic behavior in a useful temperature range (180-220 °C) for its application in vitrimers. The mechanism is found to involve 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) as an organic catalyst in the presence of hydroxyl groups. Using this new mechanistic approach, vitrimers with ultrafast stress-relaxation characteristics (relaxation times below 10 s) have been prepared with a readily available epoxy resin and siloxane-amine hardener. Subsequently, the low viscosity siloxane-containing vitrimer resin enabled the preparation of glass fiber-reinforced vitrimer composites using an industrially relevant vacuum-assisted resin infusion technique. The resulting composite was successfully thermoformed into a new shape, which makes it possible to envision a second life for such highly engineered materials.

A Highly Dynamic Covalent Polymer Network without Creep: Mission Impossible?

Dynamic covalent polymer networks provide an interesting solution to the challenging recyclability of thermosets and elastomers. One of the remaining design constraints, however, is balancing thermal reprocessability in the form of material flow with dimensional stability during use. As a result, many chemistries are being investigated in order to improve bond reactivity control and material robustness. This Minireview highlights a number of promising concepts, with a particular emphasis on disconnecting chemical reactivity in low and high temperature regimes to obtain creep resistant, yet highly dynamic polymer networks. In addition, we will highlight the impact of sharp reactivity changes when applying extrapolation-based approaches during rheological analysis. As a result, we are confident that abandoning the myth of "permanent" reactivity will aid in the development of sustainable polymeric materials that can truly combine the benefits of thermoplastic and thermoset behaviour.

Cellulose-Derived Functional Polyacetal by Cationic Ring-Opening Polymerization of Levoglucosenyl Methyl Ether.

The unsaturated bicyclic acetal levoglucosenyl methyl ether was readily obtained from sustainable feedstock (cellulose) and polymerized by cationic ring-opening polymerization to produce a semicrystalline thermoplastic unsaturated polyacetal with relatively high apparent molar mass (up to ca. 36 kg mol-1 ) and decent dispersity (ca. 1.4). The double bonds along the chain can undergo hydrogenation and thiol-ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

Ring-Opening Metathesis Polymerization of Biomass-Derived Levoglucosenol.

The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100 kg mol-1 and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 °C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.