Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts
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The Bernoullian (chain-end control) expressions in the Bovey formalism (Pmis the probability of a meso dyad) for pentad sequences are the following: [mmmm] =Pm4; [mmmr] = 2Pm3(1 −Pm); [rmmr] =Pm2(1 −Pm)2; [mmrr] = 2Pm2(1 −Pm)2; [mrmm] = 2Pm3(1 −Pm); [rmrr] = 2Pm(1 −Pm)3; [mrmr] = 2Pm2(1 −Pm)2; [rrrr] = (1 −Pm);(4) [mrrr] = 2Pm(1 −Pm)3; [mrrm] =Pm2(1 −Pm)2. The enantiomorphic site expressions in the Bovey formalism (α is the enantioface selectivity of the enantiomorphic site) for pentad sequences are the following: [mmmm] = α5+ (1 − α);(5) [mmmr] = 2[α4(1 − α) + α(1 − α)4]; [rmmr] = α3(1 − α)2+ α2(1 − α)3; [mmrr] = 2[α4(1 − α) + α(1 − α)4]; [mrmm] = 2[α3(1 − α)2+ α2(1 − α)3]; [rmrr] = 2[α3(1 − α)2+ α2(1 − α)3]; [mrmr] = 2[α3(1 − α)2+ α2(1 − α)3]; [rrrr] = α3(1 − α)2+ α2(1 − α)3; [mrrr] = 2[α3(1 − α)2+ α2(1 − α)3]; [mrrm] = α4(1 − α) + α(1 − α).(4)
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The correct pentad distribution for a perfectly hemiisotactic polymer is the following: [mmmm]:[mmmr]:[rmmr]:[mmrr]:[rrrr]:[mrrr]:[mrrm] = 3:2:1:4:3:2:1.
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