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Unusual Cross-Linked Polystyrene by Copper-Catalyzed ARGET ATRP Using a Bifunctional Initiator and No Cross-Linking Agent

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Abstract

An anomalous polystyrene gel was obtained during the copper-catalyzed “activators regenerated by electron transfer” “atom transfer radical polymerization” (ARGET ATRP) of styrene at 60–70 °C, using ascorbic acid/Na2CO3 as the reducing system and EtOAc/EtOH as the solvent mixture. The result is remarkable since no branching nor cross-linking reagents were added to the reaction mixture and their formation in situ was excluded. The anomalous PS branching, at the origin of the phenomenon, requires a generic bifunctional initiator and is mechanistically bound to termination reactions between bifunctional macroinitiators. As a matter of fact, the branching/cross-linking phenomenon loses intensity, or even disappears, under reaction conditions that cause the built-up of CuII or increase the chain polymerization rate. The temperature is also a critical variable since no branching was observed for temperatures higher than 90 °C. We believe that the route toward gelation starts with a controlled chain polymerization of styrene from the bifunctional initiator, soon integrated by a step-growth polymerization due to radical coupling of the terminal units. The progressive decrease in the number of chains and free radicals in the reaction mixture should make more and more probable the intramolecular coupling between the C−Cl ends of the remaining long and entangled chains, producing a polycatenane network.

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Acknowledgment

The authors thank Versalis (Eni) S.p.A. for financial support.

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Correspondence to Mirko Buffagni, Franco Ghelfi or Aldo Longo.

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Supporting information

The supporting information report MALLS analyses, study on the increment of initiator concentration, kinetic study with relative 1H- and 13C-NMR spectra, polymerizations in presence of MCA, synthesis and NMR spectra of deuterated PS, selected GPC eluograms, and 1H-NMR spectra of the dehydroclorination test on the α, ω-dichloropolystyrene. The materials are available via the Internet at http://www.springer.com/13233.

Author Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Niccolò Braidi, Mirko Buffagni, Franco Ghelfi, Francesca Parenti, Maria Letizia Focarete, Chiara Gualandi, Elena Bedogni, Luisa Bonifaci, Gianfranco Cavalca, Angelo Ferrando, Aldo Longo, Ida Morandini and Nicolò Pettenuzzo. The first draft of the manuscript was written by Franco Ghelfi and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Braidi, N., Buffagni, M., Buzzoni, V. et al. Unusual Cross-Linked Polystyrene by Copper-Catalyzed ARGET ATRP Using a Bifunctional Initiator and No Cross-Linking Agent. Macromol. Res. 29, 280–288 (2021). https://doi.org/10.1007/s13233-021-9039-y

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  • DOI: https://doi.org/10.1007/s13233-021-9039-y

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