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- W1974959036 abstract "Abstract Anionic polymerization of methyl methacrylate (MMA) initiated with late transition‐metal halides [manganese chloride (MnCl 2 ), iron dichloride (FeCl 2 ), iron trichloride (FeCl 3 ), cobalt chloride (CoCl 2 ), or nickel bromide (NiBr 2 )]/organolithium [ n Butyllithium ( n BuLi) or phenyllithium (PhLi)]/triisobutylaluminum (iBu 3 Al) systems is described. Except for the system with NiBr 2 , the polymerizations of MMA afforded narrow molecular weight distribution poly(methyl methacrylate)s (PMMAs) with high molecular weights in quantitative yields at 0 °C in toluene. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) analyses of the PMMAs obtained by the systems with FeCl 2 , FeCl 3 , and CoCl 2 revealed that the polymers had hydrogen (H) at both chain ends. Accordingly, the reaction of the transition‐metal halides with the organolithium in the presence of iBu 3 Al should result in the formation of transition‐metal hydride [M‐H] − species, which was nucleophilic enough to initiate the MMA polymerization. Because the presence of a six‐membered cyclic structure resulting from backbiting was confirmed from the MALDI‐TOF MS analyses of the PMMA obtained with the metal halide (FeCl 2 , FeCl 3 , or CoCl 2 )/organolithium systems in the absence of iBu 3 Al, the introduction of H at the ω‐chain end indicated that iBu 3 Al should prevent the backbiting. However, the MnCl 2 / n BuLi/iBu 3 Al initiating system gave PMMAs bearing H at the α chain end and six‐membered cyclic structure at the ω chain end. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1962–1977, 2003" @default.
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- W1974959036 date "2003-05-19" @default.
- W1974959036 modified "2023-10-15" @default.
- W1974959036 title "Anionic polymerization of methyl methacrylate initiated with late transition-metal halides/organolithium/triisobutylaluminum systems" @default.
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- W1974959036 doi "https://doi.org/10.1002/pola.10737" @default.
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