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Atom transfer radical polymerization by [RuCl2(PPh3)2(amine)] catalysts: Cyclic amines as tuner of reactivity

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Abstract

Atom transfer radical polymerizations (ATRP) of styrene (St) and methyl methacrylate (MMA) mediated by [RuCl2(PPh3)2(amine)] complexes, with amine = pyrrolidine (1), piperidine (2), or perhydroazepine (3), were investigated as a function of time, temperature, and concentrations of monomers and 2-bromoisobutyrate as initiator. The plots of ln([M]0/[M]) vs. time and molecular weights vs. monomer conversion were linear and the dispersity indexes decreased with increasing monomer conversions. The complexes 1, 2, and 3 were able to mediate the polymerizations with acceptable rate and level of control. Differences in the rate and control of polymerization were observed in the order 3 > 2 > 1 for both monomers. The activities were discussed considering the steric hindrance and electronic characteristics of the amines as ancillary ligands in the metal centres, considering studies by cyclic voltammetry and NMR.

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Acknowledgements

The authors are indebted to the financial support from FAPESP (Proc. 2013/10002-0).

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Authors and Affiliations

  1. Faculdade de Ciências e Tecnologia, UNESP Univ Estadual Paulista, Presidente Prudente, SP, 19060-900, Brazil

    Thais R. Cruz, Patrícia Borim, Beatriz E. Goi & Valdemiro P. Carvalho Jr

  2. Instituto de Química de São Carlos, Universidade de São Paulo, São Carlos, SP, 13560-970, Brazil

    Patrícia Borim & Benedito S. Lima-Neto

  3. Centro de Ciências da Natureza, Universidade Estadual do Piauí, Teresina, PI, 64002-150, Brazil

    José L. Silva Sá

Authors
  1. Thais R. Cruz
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  2. Patrícia Borim
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  3. Beatriz E. Goi
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  4. José L. Silva Sá
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  5. Benedito S. Lima-Neto
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  6. Valdemiro P. Carvalho Jr
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Correspondence to Benedito S. Lima-Neto or Valdemiro P. Carvalho Jr.

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Cruz, T.R., Borim, P., Goi, B.E. et al. Atom transfer radical polymerization by [RuCl2(PPh3)2(amine)] catalysts: Cyclic amines as tuner of reactivity. J Polym Res 24, 196 (2017). https://doi.org/10.1007/s10965-017-1354-9

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  • DOI: https://doi.org/10.1007/s10965-017-1354-9

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