Synthesis of Ultrahigh Molecular Weight Poly (Trifluoroethyl Methacrylate) Initiated by the Combination of Palladium Nanoparticles with Organic Halides

Ultrahigh molecular weight polymers display outstanding properties and have great application potential. However, the traditional polymerization methods have inevitable disadvantages that challenge the green synthesis of ultrahigh molecular weight polymers. The paper achieved an ultrahigh molecular weight poly (trifluoroethyl methacrylate) via a novel polymerization and discussed the mechanistic, kinetic, and experimental aspects. The combination of palladium nanoparticles with ethyl 2-bromopropionate has been identified as an exceedingly efficient system for initiating the polymerization of trifluoroethyl methacrylate. An ultrahigh molecular weight poly (trifluoroethyl methacrylate) with a number-average molecular weight up to 3.03 × 10⁶ Da has been synthesized at a feeding molar ratio of [poly (trifluoroethyl methacrylate)]/[ethyl 2-bromopropionate]/[palladium nanoparticles] = 3.95 × 10⁴:756:1 at 70 °C. The reaction orders concerning palladium nanoparticles, ethyl 2-bromopropionate, and poly (trifluoroethyl methacrylate) were determined to be 0.59, 0.34, and 1.38, respectively. By analyzing a series of characterizations, we verified that the polymerization of poly (trifluoroethyl methacrylate) was initiated by the ethyl 2-bromopropionate residue radicals, which were generated from the interaction between palladium nanoparticles and ethyl 2-bromopropionate. The comparatively large size of the palladium nanoparticles provided a barrier to chain-growing radicals, promoting the synthesis of ultrahigh molecular weight polymers.