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Half-sandwich samarium(III) diketiminate bromide was successfully synthesized and was shown to be active in methyl methacrylate (MMA) polymerization. The effects of temperature, polymerization time and catalyst concentration were studied. Activities of ca. 18kg of polymethacrylate (PMMA) per mol of samarium per hour were obtained under optimum conditions (0°C and a MMA/catalyst molar ratio of 100/1), giving a polymer with a molar mass M n >24,000gmol −1 and a molar mass distribution (M w /M n )<1.4. After 1h of polymerization, conversions of MMA as high as 96% were observed.
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