Polymer/mosquito-repellent scaffolds exhibit increasing importance in long-lasting human skin protection to be used as wearable devices and allowing for controlled release of repellents. In this study, ethyl butylacetylaminopropionate (IR3535) was used as a human and environmental friendly active mosquito-repellent serving as a solvent to form functional poly­(l-lactic acid) (PLLA) scaffolds by crystallization-based solid–liquid thermally induced phase separation. Crystallization of PLLA in the presence of IR3535 is faster than melt-crystallization of neat PLLA, and in the investigated concentration range from 5 to 50 mass % PLLA, its maximum crystallization rate increases with the PLLA content, by both, increases of the maximum crystal growth rate and of the nuclei density. By adjusting the polymer concentration and the crystallization temperature, microporous scaffolds of different fine structures are obtained, hosting the mosquito-repellent in intra- and interspherulitic pores for its intended later evaporation.

Poly(butylene succinate) (PBS) is used to produce micro-/nanoporous biodegradable scaffolds, suitable for the release of the mosquito repellent N,N-diethyl-3-methylbenzamide (DEET), based on thermally induced phase separation. For solvent-rich compositions up to 30 m% PBS, it was found that PBS dissolves in DEET at elevated temperatures. During cooling, spherulitic crystallization of PBS occurs, with the crystallization temperature decreasing with the content of DEET and the cooling rate, as determined by cloud-point measurements, differential scanning calorimetry, and polarized-light optical microscopy. Scaffold morphologies of quenched solutions were analyzed by scanning electron microscopy as a function of the polymer concentration and the quenching temperature. These two parameters control the nucleus density/spherulite size, the degree of intermeshing of spherulites, and the intra- and interspherulitic pore size, with the latter typically being of the order of magnitude of few micrometers.

Bio-sourced and biodegradable poly(butylene succinate) (PBS) strands containing up to 40 m% mosquito-repellent N,N-diethyl-3-methylbenzamide (DEET) were obtained by extrusion, for an initial evaluation of the DEET evaporation characteristics and the possible application of such strands as biodegradable slow-release repellent-delivery devices. For DEET concentrations up to 20 m%, DEET is entrapped in the semicrystalline spherulitic superstructure of PBS. In contrast, at higher DEET concentrations, the liquid repellent, at least partially, is not fully incorporated in the PBS spherulites rather than segregates to form an own macrophase. Quantification of the release of DEET to the environment by thermogravimetric analysis at different temperatures between 60 and 100 °C allowed estimation of the evaporation rate at lower service temperatures, suggesting an extremely low release rate with a time constant of the order of magnitude of 1−2 years at 25 °C, independent of the initial concentration.