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Lithium naphthalenides in non-polar or in low-polarity media: some insights regarding their use as initiators in anionic polymerizations

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Abstract

The synthesis of bidirectional anionic initiators by the reaction between metallic lithium (Li) and naphthalene (Naph), under mild conditions, in non-polar (benzene) or low-polarity media (benzene/THF mixtures) is reported. The efficiency of these initiators to provide macromolecules with well-defined structures was demonstrated. Model linear homopolymers from styrene (S) or hexamethyl(ciclotrisiloxane) (D3) monomers were synthesized using classical anionic polymerization (high-vacuum techniques). The model polymers obtained were analyzed using the conventional analytical techniques, and showed narrow molar mass distributions, a broad range of molar masses (from 3000 to 1,000,000 g/mol) and polydispersity indexes (M w/M n) lower than 1.1. High molar mass polymers were obtained using pure benzene as solvent, whereas lower molar masses were obtained in benzene/THF mixtures in which the concentration of THF was lower than 10 % v/v. The ratio [Li]/[Naph] and the nature of the reaction medium are the experimental parameters to be controlled to obtain the desired lithium naphthalenides.

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Acknowledgments

We express our gratitude to the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina (CONICET), the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT), and the Universidad Nacional del Sur (UNS, Argentina) for their financial support. The authors also wish to thank Dr. Cristian Vitale for the 1H-NMR spectrum and his helpful advices in the analysis.

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Authors and Affiliations

  1. Planta Piloto de Ingeniería Química (PLAPIQUI), Departamento de Ingeniería Química, Universidad Nacional del Sur (UNS), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Camino “La Carrindanga” Km. 7, 8000, Bahía Blanca, Argentina

    Mario D. Ninago, María Loreta Sena Marani, Verónica A. González, Angel J. Satti, Claudia Sarmoria, Marcelo A. Villar, Enrique M. Vallés & Andrés E. Ciolino

  2. Departamento de Química, Instituto de Química del Sur (INQUISUR), UNS, CONICET, Av. Alem 1253, 8000, Bahía Blanca, Argentina

    Angel J. Satti

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  1. Mario D. Ninago
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Correspondence to Angel J. Satti.

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Ninago, M.D., Marani, M.L.S., González, V.A. et al. Lithium naphthalenides in non-polar or in low-polarity media: some insights regarding their use as initiators in anionic polymerizations. Polym. Bull. 74, 307–323 (2017). https://doi.org/10.1007/s00289-016-1715-2

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