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The polyaddition, chain, and polycondensation machanisms of formation of networks based on bismaleimides
Author(s) -
Rozenberg Boris A.,
Dzhavadyn Emma A.,
Morgan Roger J.,
Shin Eugene E.
Publication year - 2001
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/1521-3900(200106)171:1<87::aid-masy87>3.0.co;2-3
Subject(s) - maleimide , chemistry , branching (polymer chemistry) , polymer chemistry , polymerization , propenyl , condensation polymer , steric effects , reaction mechanism , kinetics , organic chemistry , polymer , catalysis , physics , quantum mechanics
The kinetics and mechanisms of polymerization ofequifunctional4,4'‐(N,N'‐bismaleimide)‐diphenylmethane/2,2'‐diallyl‐bisphenolA (BMDM/DABPA) and model(phenylmaleimide/2‐allylphenol)(PMI/AP) systems have been studied in the temperaturerange 140 – 400 °C using IR‐, 1 H and 13 C NMR spectroscopy, GC/MS, DSC, and isothermalcalorimetry. It was established that the cure mechanism consisted of aunique combination of step‐wise and chain polymerization ofmaleimide and propenyl groups generated by the first reaction. Thelast reaction was the main branching reaction. The second source ofbranching was the dehydration reaction of phenol groups(polycondensation reaction) that proceeds with theparticipation of the 1:1 “ene” adduct as one of thecomponent. Homopolymerization of maleimide groups proceededautocatalytically, initiated by free radicals generated by thermaldecomposition of the maleimide‐propenyl group'sdonor–acceptor pairs. The steric hindrance in2,2'‐diallyl‐bisphenol A prevented the reversibleDiels–Alder reaction, but the reaction proceeded in modelsystems. Some thermodynamic and kinetics parameters of the reactionshave been determined.