ISSN:
0887-624X
Keywords:
methyl methacrylate
;
redox polymerization
;
kinetics
;
mechanism
;
additives
;
iron saccharinate
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The role of N,N-dimethyl-p-toluidine (DMPT) and saccharin as accelerators in the polymerization of methyl methacrylate initiated by the redox decomposition of cumene hydroperoxide (CHP) in the presence of iron saccharinate has been kinetically investigated. DMPT reduces ferric ions to ferrous ions, so that an equilibrium is established between the two oxidation states. With the assumption of a steady-state concentration of propagating radicals, the rate of initiation was deduced from the rate of polymerization and the kinetic orders with respect to each compound involved in the initiation step have been determined. The reaction is first-order in CHP, iron saccharinate, and saccharine and second-order in DMPT. In a proposed scheme, Fe2+ ions, complexed by two DMPT molecules, are much more reactive than uncomplexed Fe2+ and saccharin activates the decomposition of CHP by protonation of the O—O bond. This mechanism, similar to that proposed in the case of copper saccharinate, explains the synergistic effect of both accelerators. © 1994 John Wiley & Sons, Inc.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1994.080320808
Permalink
