Epoxy-anhydride vitrimers are covalent adaptable networks, which undergo associative bond exchange reactions at elevated temperature. Their service temperature is influenced by the glass transition temperature (Tg) as well as the topology freezing transition temperature (Tv), at which the covalent bond exchange reactions become significantly fast. The present work highlights the design of high-Tg epoxy-anhydride vitrimers that comprise an efficient stress relaxation at elevated temperature. Networks are prepared by thermally curing aminoglycidyl monomers with glutaric anhydride in different stoichiometric ratios. The tertiary amine groups present in the structure of the aminoglycidyl derivatives not only accelerate the curing reaction but also catalyse the transesterification reaction above Tv, as shown in stress relaxation measurements. The topology rearrangements render the networks recyclable, which is demonstrated by reprocessing a grinded powder of the cured materials in a hot press. The epoxy-anhydride vitrimers are characterised by a high Tg (up to 140 °C) and an adequate storage modulus at 25 °C (~2.5 GPa), which makes them interesting candidates for structural applications operating at high service temperature.
The present work highlights a new approach to write, erase, and rewrite micropatterns into the same region of covalent adaptable polymer networks. Thermal curing of an epoxy‐terminated o‐nitrobenzyl ester (o‐NBE) derivative with hexahydrophthalic anhydride in the presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene yields a dynamic covalent network, whose solubility is locally controlled by irradiation with ultraviolet (UV) light. The photolysis of the o‐NBE chromophores enables a well‐defined cleavage of the epoxy‐anhydride network, and the formation of soluble photolysis products is confirmed by sol‐gel analysis. The photo‐induced change in solubility is exploited to inscribe micropatterns by photolithographic techniques and after development in an organic solvent positive tone structures with a feature size of 20 µm are obtained. Due to the thermo‐activated exchange reactions of the hydroxyl ester links and the related macroscopic reflow, the polymer patterns are fully erased at temperatures well above the topological freezing transition of the vitrimer network. The regenerated film has a smooth surface topology and can be reused to inscribe new micropatterns via mask lithography.
The present work provides a comparative study on the photopatterning of epoxy-based thermosets as a function of network structure and network mobility. Local switching of solubility properties by light of a defined wavelength is achieved by exploiting versatile o-nitrobenzyl ester (o-NBE) chemistry. o-NBE derivatives with terminal epoxy groups are synthetized and thermally cured with different types of cycloaliphatic anhydrides via nucleophilic ring opening reaction. By varying the structure of the anhydride, glass transition temperature (Tg) and surface hardness are adjusted over a broad range. Once the network has been formed, the photolysis of the o-NBE groups enables a well-defined degradation of the 3D network. Fourier transform infrared (FT-IR) spectroscopy studies demonstrate that cleavage rate and cleavage yield increase with rising mobility of the network, which is either facilitated by inherent network properties (Tg below room temperature) or a simultaneous heating of the thermosets above their Tg. The formation of soluble species is evidenced by sol-gel analysis, revealing that low-Tg networks are prone to secondary photoreactions at higher exposure doses, which lead to a re-crosslinking of the cleaved polymer chains. The change in solubility properties is exploited to inscribe positive tone micropatterns within the thermosets by photolithographic techniques. Contrast curves show that the resist performance of rigid networks is superior to flexible ones, with a contrast of 1.17 and a resolution of 8 µm.
The present work highlights the synthesis and post-modification of silica-based micro-particles containing photo-responsive polymer brushes with photolabile o-nitrobenzyl ester (o-NBE) chromophores. For the synthesis of the polymer brushes, two different...
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