Polymer micronetworks allowing stimuli-induced, predefined, and spatially directed shape shifts. The temperature-induced on-demand switching of shape is introduced as a function of polyester carriers. With their adjustable -switching temperature, micronetworks may serve as a model system to explore static and dynamic shape effects in biological systems.

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In this work, a novel type of polyester urethane urea (PEUU) foam is introduced. The foam was produced by reactive foaming using a mixture of poly(1,10–decamethylene adipate) diol and poly(1,4–butylene adipate) diol, 4,4′-diphenylmethane diisocyanate, 1,4–butanediol, diethanolamine and water as blowing agent. As determined by differential scanning calorimetry, the melting of the ester-based phases occurred at temperatures in between 25 °C and 61 °C, while the crystallization transition spread from 48 °C to 20 °C. The mechanical properties of the foam were simulated with the hyperplastic models Neo-Hookean and Ogden, whereby the latter showed a better agreement with the experimental data as evidenced by a Pearson correlation coefficient R² above 0.99. Once thermomechanically treated, the foam exhibited a maximum actuation of 13.7% in heating-cooling cycles under a constant external load. In turn, thermal cycling under load-free conditions resulted in an actuation of more than 10%. Good thermal insulation properties were demonstrated by thermal conductivities of 0.039 W·(m·K)−1 in the pristine state and 0.052 W·(m·K)−1 in a state after compression by 50%, respectively. Finally, three demonstrators were developed, which closed an aperture or opened it again simply by changing the temperature. The self-sufficient material behavior is particularly promising in the construction industry, where programmable air slots offer the prospect of a dynamic insulation system for an adaptive building envelope.

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Microfluidic droplet templating produces monodisperse particles of well controllable sizes, but this is limited by the necessity to operate microfluidic devices at low flow rates in the dripping regime. Here, the per-channel rate of droplet production could be substantially increased by delayed surfactant addition as applied and verified for microfluidic production of N-isopropylacrylamide based microgels.

The crosslinking condition of methacrylate functionalized precursors significantly affected network properties. For some types of precursors such as star-shaped telechelics, synthesis in solution provided semi-crystalline elastic materials that were not accessible from crosslinking in melt.

*Polyester networks can be prepared by ultraviolet (UV)-light-induced radical polymerization of methacrylate functionalized oligo(ε-caprolactone)s. The properties and functions of the obtained materials depend on defined network structures and may be altered, if crosslinking would occur by side reactions in other positions than the methacrylate endgroups. In order to explore whether and to which extent such side reactions occur, network synthesis as well as related model reactions were performed in the absence of photoinitiator. Hereby precursor structures (linear and four-arm star-shaped) and reaction conditions (in solution and in the melt) were varied. Unspecific side reactions were found only upon extensive UV irradiation for 60 min (26 mW cm -2 ) with minor but detectable alterations of physicochemical properties of the networks. The analysis of model reactions suggested minor photolytic cleavage of ester bonds during polymer network synthesis. However, the effect of these side reactions on network properties and functions appeared to be less relevant than an incomplete precursor integration because of a too short UV irradiation for crosslinking.

A switching pattern of polymer micronetwork (MN) particles towards increased rather than the common decreased aspect ratios has been realized. This feature is based on the programming of MN during the shape recovery of a second shape memory polymer.