Non-ideal polymerization kinetics of a cationic double charged acryl monomer and solution behavior of the resulting polyelectrolytes

The radical polymerization of bis-1,3(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride revealed non-ideality with 0.59 and 4.4 for the reaction orders of the initiator and monomer concentration, respectively. Further, autoacceleration was observed from less than 10% conversion onwards. Degradative chain transfer to the monomer was concluded to explain the initiator exponent. Mono- mer association and electrostatic effects are hypothesized to govern the monomer exponent and autoacceleration. The exponential concentration dependent increase of the viscosity of the monomer solution and the relatively low overall activation energy Ea ¼ 31.5 kJ•mol-1 support the hypothesis. Counterion activity measurements confirmed strong counterion conden- sation as expected for a charge distance of 0.12 nm.