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An experimental study on the kinetics of nitroxide‐mediated free radical copolymerization (NMRP) of styrene (STY) and divinylbenzene (DVB) is presented. The experiments were carried out in bulk from a mixture of monomers, stable free radical controller (2,2,6,6‐Tetramethyl‐1‐piperidinyloxy, TEMPO), and initiator (dibenzoyl peroxide, BPO), at 120°C, without using a TEMPO‐capped prepolymer in the initial mixture. The system studied is a case of bimolecular NMRP, as opposed to the monomolecular NMRP of styrene and other crosslinker previously addressed in the literature by others. The results on total monomer conversion (polymerization rate), molecular weight development, gel fraction, and swelling index are compared against a conventional reference system (a STY/DVB copolymer, also synthesized for this study). No significant auto‐acceleration effect was observed in the early and intermediate conversion ranges of the TEMPO‐controlled copolymerization of STY/DVB, and the gelation point was significantly delayed.
†On research leave from UNAM.
Acknowledgements
The authors would like to acknowledge financial support from the National Sciences and Engineering Research Council (NSERC, Canada), Consejo Nacional de Ciencia y Tecnología (CONACYT, México, Project CIAM U40259‐Y), and CNPq (Brazil), through the special Inter American Materials Collaboration (IAMC or CIAM) joint project. E. V.‐L. gratefully acknowledges Dirección General de Asuntos del Personal Académico (DGAPA) of Universidad Nacional Autónoma de México (UNAM) (PASPA Program) and the Department of Chemical Engineering of the University of Waterloo for the financial support received during his research stay at the University of Waterloo. AP would also like to thank the Canada Research Chair (CRC) program of NSERC.
Notes
†On research leave from UNAM.