Premium
Non‐Ideal Polymerization Kinetics of a Cationic Double Charged Acryl Monomer and Solution Behavior of the Resulting Polyelectrolytes
Author(s) -
Losada Ricardo,
Wandrey Christine
Publication year - 2008
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200700670
Subject(s) - monomer , cationic polymerization , counterion , polymerization , polymer chemistry , polyelectrolyte , kinetics , counterion condensation , chemistry , chain transfer , materials science , radical polymerization , polymer , organic chemistry , ion , physics , quantum mechanics
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. Monomer 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 E a = 31.5 kJ · mol −1 support the hypothesis. Counterion activity measurements confirmed strong counterion condensation as expected for a charge distance of 0.12 nm.