Reversible shape-memory properties of surface functionalizable, crystallizable crosslinked terpolymers


There is a high demand for polymer actuators comprising reactive groups at their surface in biotechnological or bioanalytical devices especially in microfluidics. In this work, we explored whether a thermoplastic poly[ethylene-co-(ethyl acylate)-co-(maleic anhydride)] (PEEAMA) terpolymer can be converted to a multifunctional shape-memory actuator by introducing covalent netpoints. In crosslinked PEEAMA (cPEEAMA) crystalline polyethylene (PE) domains with melting temperatures below 70°C should serve as actuation domains, responsible for the reversible shape change during cyclic heating and cooling, while higher melting PE crystals act as skeleton forming domains; finally maleic anhydride (MAH) groups enable surface modification of the polymeric substrate. cPEEAMAs with a fixed composition and various crosslink densities were prepared by thermally crosslinking of PEEAMA using different dicumyl peroxide (DCP) concentrations in the starting reaction mixture. A broad melting transition in the range of 50 to 90°C with a melting temperature interval of ∆Tm = 40°C, related to the crystalline PE domains, was observed for all polymer networks in differential scanning calorimetric experiments. Cyclic, thermomechanical uniaxial tensile tests revealed high reversible strains up to 17 ± 2%. A reversible change in long period during repetitive heating and cooling was observed in in situ small angle X-ray scattering experiments. Finally, a successful functionalization of the MAH groups at the cPEEAMA surface by reaction with ethylene diamine was confirmed by infrared spectroscopy analysis. The presented amino functionalized cPEEAMA substrates could be a candidate material for the preparation of adaptive microfluidic devices.
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