1998
DOI: 10.1002/(sici)1099-0518(19981115)36:15<2785::aid-pola15>3.0.co;2-k
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Kinetic investigations on the photopolymerization of di- and tetrafunctional methacrylic monomers in polymeric matrices. ESR and calorimetric studies. II. Postpolymerization reactions

Abstract: The reaction kinetics in the dark of photopolymerized mono‐ and dimethacrylates in a polymeric binder has been studied. Electron spin resonance spectroscopy (ESR) provided useful information regarding the nature of the radicals involved in postpolymerization reactions. Computer simulations were performed to study the decay of the propagating radicals by considering normal bimolecular termination and transfer reactions of the radicals to the binder. Differences were found in the termination reactions for mono‐ … Show more

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Cited by 13 publications
(5 citation statements)
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“…All the systems studied, even those with low monomer concentrations (10 and 20%), yielded cross-linked structures when they were polymerized, which indicates that the SBS matrix participates appreciably in the polymerization process. This participation takes place, according to previous studies, [21][22][23] and results were obtained here, through hydrogen abstraction in the allylic and benzylic positions of the SBS matrix and by the direct addition of the growing macroradical and the primary radical from the photoinitiator to the double bond of the polybutadiene moiety.…”
Section: Analysis and Discussionsupporting
confidence: 62%
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“…All the systems studied, even those with low monomer concentrations (10 and 20%), yielded cross-linked structures when they were polymerized, which indicates that the SBS matrix participates appreciably in the polymerization process. This participation takes place, according to previous studies, [21][22][23] and results were obtained here, through hydrogen abstraction in the allylic and benzylic positions of the SBS matrix and by the direct addition of the growing macroradical and the primary radical from the photoinitiator to the double bond of the polybutadiene moiety.…”
Section: Analysis and Discussionsupporting
confidence: 62%
“…These results have been useful to analyze photopolymerization profiles using DSC and ESR as monitoring techniques in methacrylic monomer-SBS matrix-photoiniator systems and to identify the photogenerated radicals. 22,23 Allylic and benzylic radicals were detected, and the methacrylic radical is found to propagate from the beginning of the reaction in a state of restricted mobility, thus confirming that the mechanism of photopolymerization in polymeric binders takes place through reaction diffusion.…”
Section: Introductionmentioning
confidence: 67%
“…5) supports a bimolecular mechanism for their decay that is not complicated by the presence of a monomolecular mechanism (as noted in ref. 19) or by the dependence of k t on time (as observed in ref. 18):…”
Section: Resultsmentioning
confidence: 91%
“…D 0 is determined by eq. (19) and is definitely applicable to polymeric chains in diluted solutions. It follows from the same position that a constant rate of bimolecular chain termination under diffusion conditions in diluted solutions [as follows from eq.…”
Section: Theoretical Predictionmentioning
confidence: 99%
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