A contribution to the kinetics of the polymerization of styrene with CF3SO3H as catalyst

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.

Measurements on the temperature dependence of the cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst

The cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst and at low monomer concentrations shows, at −15°C, −45°C and −60°C, the same formal dependence on monomer concentration. The dependence on the catalyst concentration is approximately but not exactly of a third order.

Polymerization of styrene