RESUMO
As a result of the search for alternatives to the known methods for the synthesis of PLA/vinyl polymer block copolymers, a new approach based on the "iniferter" concept was demonstrated in this article. In this approach, the introduction of a group that was capable of forming radicals and initiating radical polymerization into the polylactide (PLA) chain was conducted. Then, the obtained functional PLA was heated in the presence of a radically polymerizable monomer. The tetraphenylethane (TPE) group was chosen as a group that could dissociate to radicals. PLA with a TPE group in the middle of the chain was prepared in several steps as follows: (1) the synthesis of 4-(2-hydroxyethoxy)benzophenone (HBP-ET); (2) the polymerization of lactide, which was initiated with HBP-ET; and (3) the coupling of HBP-ET chains under UV radiation to form TPE-diET_PLA. A "macroiniferter", i.e., TPE-diET_PLA, was used to initiate the polymerization of acrylonitrile (AN) by heating substrates at 85 °C. 1H and 13C NMR and SEC analyses of the products indicated that the triblock copolymer PLA-PAN-PLA formed and thus confirmed the assumed mechanism of the initiation of AN polymerization, which relied on the addition of the radical that formed from TPE (linked with the PLA chain) to the monomer molecule. Copolymerizations were performed with the application of prepared TPE-diET_PLA with three different Mn's (1400, 2200, and 3300) and with different AN/PLA ratios, producing copolymers with varied compositions, i.e., with AN/LA ratios in the range of 2.3-11.1 and Mn's in the range of 5100-9400. It was shown that the AN/LA ratio in the copolymer was increasable by the applied excess of AN with respect to the PLA macroiniferter in the feed and that more AN monomer was able to be introduced to PLA with shorter chains.
RESUMO
Polylactide (PLA) is presently the most studied bioderived polymer because, in addition to its established position as a material for biomedical applications, it can replace mass production plastics from petroleum. However, some drawbacks of polylactide such as insufficient mechanical properties at a higher temperature and poor shape stability have to be overcome. One of the methods of mechanical and thermal properties modification is crosslinking which can be achieved by different approaches, both at the stage of PLA-based materials synthesis and by physical modification of neat polylactide. This review covers PLA crosslinking by applying different types of irradiation, i.e., high energy electron beam or gamma irradiation and UV light which enables curing at mild conditions. In the last section, selected examples of biomedical applications as well as applications for packaging and daily-use items are presented in order to visualize how a variety of materials can be obtained using specific methods.
