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One-Step Radical-Induced Synthesis of Graft Copolymers for Effective Compatibilization of Polyethylene and Polypropylene

The synthesis of copolymers from high-density polyethylene (HDPE) and isotactic polypropylene (iPP) has gained increasing attention due to their ability to improve the recycling of incompatible mixed polyolefin waste feed streams. Herein, we report a new radical grafting process that yields HDPE-g-iPP copolymers from HDPE and iPP by using a commercially available peroxide. Tensile testing of brittle 70/30 HDPE/iPP mixtures with these graft copolymers added showed promising compatibilization, improving the elongation at break of the blends from 20% up to 1080%. Detailed kinetic studies coupled with thermal and rheological characterization revealed optimized conditions for HDPE and iPP macroradical coupling and a deeper understanding of the grafting reaction. This optimization yielded HDPE-g-iPP copolymers that compatibilize HDPE and iPP blends at loadings as low as 2.5 wt %. In conclusion, the versatility of this macroradical grafting reaction was demonstrated by preparing an effective compatibilizer from untreated postconsumer waste plastics.

compatibilization↗

Organo-catalyzed deamination of polystyrene sulfonamide for diverse post-polymerization modification of styrenic polymers

Post-polymerization modification allows for the incorporation of functional groups that would otherwise be incompatible with polymerization conditions, enhancing synthetic efficiency and facilitating the creation of complex polymer architectures for specialized applications, such as biomedical devices, electronics, and advanced coatings. Herein, we report a method inspired by late-stage functionalization of small molecules for the post-polymerization modification of aromatic polymers, specifically polystyrene (PS), under mild reaction conditions. First, PS was converted to polystyrene sulfonamide (PSSNH 2 ) with an 85% yield using established procedures. PSSNH 2 was subsequently transformed into a reactive sulfinate by deamination using an N-heterocyclic carbene (NHC) catalyst and benzaldehyde. The catalytic process was optimized by varying catalysts, solvents, bases, temperatures, and reaction times. The highest degree of deamination was 88% with a bicyclic NHC and K 2 CO 3 base in DMSO for 18 hours at 120 °C. The reactive sulfinate was then treated with various functional reagents, resulting in a library of aromatic polymers with different substituents with high degrees of functionalization ranging from 74% to 98%. Similarly, we modified expanded PS waste with trifluorobutyl iodide with a degree of functionalization of 72%, highlighting a new avenue for plastic upgrading. This approach could be used to rapidly generate functionalized polymers from PS with potential applications, including antibacterial properties and flame retardancy.

Shrestha, Tulaja [Univ. of Delaware, Newark, DE (U↗