Abstract
The time dependence of the cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst can be formally described as being first-order with respect to monomer concentration [M]0. The reaction rate shows a third-order dependence in catalyst concentration [C]0. A high polymer and a low polymer polystyrene fraction are found at [M]0>0.2 mole · l−. The reaction rate of the high polymer fraction is proportional to [C] 0 3 , that of the low polymer fraction probably proportional to [C] 0 2 . The polymerization active species may thus be triple ions in the first and ion pairs in the second case.
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