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• W2056340314 abstract "The quantity kp/k-i was measured from first-order kinetic data for cationic quasiliving polymerization of styrene and isobutylene initiated with 5-tert-butyl-1,3-bis(2-chloro-2-propyl)benzene (bDCC)/TiCl4 in 60/40 MCHex/MeCl, via analysis of an initiation event termed rapid monomer consumption (RMC). RMC is characterized by an initial period of high polymerization rate followed by slower first-order decay in monomer concentration and is due to a larger ionization rate for the initiator compared to the polymer chain end. The value of kp/k-i was used in conjunction with the apparent rate constant for propagation, kapp, to calculate apparent rate constants of chain-end ionization, ki, for both monomers at −60, −70, −80, and −90 °C, independently of kp. Rate constants of ion-pair collapse and ionization equilibrium were calculated assuming published values of kp. Apparent energies of activation for kp/k-i of −2.4 and −4.6 kcal/mol were determined for styrene and IB, respectively. Apparent energies of activation for ionization, propagation, and ionization equilibrium were calculated for both monomers. Rates of chain-end ionization and ion-pair collapse were both higher and more sensitive to temperature for polyisobutylene than polystyrene." @default.
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• W2056340314 date "2005-05-12" @default.
• W2056340314 modified "2023-10-14" @default.
• W2056340314 title "Quasiliving Cationic Polymerization of Styrene and Isobutylene: Run Number and Apparent Rate Constant of Ionization by TiCl₄ and Energies of Activation of Elementary Reactions" @default.
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• W2056340314 doi "https://doi.org/10.1021/ma050470j" @default.
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