Synthesis of Ultrahigh Molecular Weight Poly(methyl Methacrylate) via the Polymerization of MMA Initiated by the Combination of Palladium Carboxylates with Thiols

A novel synthesis of ultrahigh molecular weight poly(methyl methacrylate) (PMMA) using organosulfur compounds combined with a catalytical amount of transition metal carboxylates as an initiator has been developed. The combination of 1-octanethiol with palladium trifluoroacetate (Pd(CF(3)COO)(2)) was found to be a very efficient initiator for the polymerization of methyl methacrylate (MMA). An ultrahigh molecular weight PMMA with a number-average molecular weight of 1.68 × 10(6) Da and a weight-average molecular weight of 5.38 × 10(6) Da has been synthesized at the optimal formulation of [MMA]:[Pd(CF(3)COO)(2)]:[1-octanethiol] = 94,300:8:23 at 70 °C. A kinetic study showed that the reaction orders with respect to Pd(CF(3)COO)(2), 1-octanethiol, and MMA are 0.64, 1.26, and 1.46, respectively. A variety of techniques such as proton nuclear magnetic resonance spectroscopy ((1)H NMR), electrospray ionization mass spectroscopy (ESI-MS), size exclusion chromatography (SEC), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and electron paramagnetic resonance spectroscopy (EPR) were employed to characterize the produced PMMA and palladium nanoparticles (Pd NPs). The results revealed that Pd(CF(3)COO)(2) was firstly reduced by the excess of 1-octanethiol to form Pd NPs at the early stage of the polymerization, followed by the adsorption of 1-octanethiol on the surface of nanoparticles and subsequent generation of corresponding thiyl radicals to initiate the polymerization of MMA.