Copolymerization of ethylene with unsaturated alcohols and methylmethacrylate using a silylated α-diimine nickel catalyst: Molecular modeling and photodegradation studies

Authors

  • Inês Matos,

    1. Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
    2. REQUIMTE/CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
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  • Susete N. Fernandes,

    1. Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
    2. CENIMAT/I3N, Departamento de Ciência dos Materiais, Faculdade de Ciências e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
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  • Hua-Rong Liu,

    1. Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
    2. Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, People's Republic of China
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  • Amit K. Tevtia,

    1. Polymer Chemistry Division, National Chemical Laboratory, Pune 411008, India
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  • R. P. Singh,

    Corresponding author
    1. Advanced Research Centre in Pharmaceutical Sciences and Applied Chemisty, Bharati Vidyapeeth University, Erandawane, Pune 411038, India
    • Advanced Research Centre in Pharmaceutical Sciences and Applied Chemisty, Bharati Vidyapeeth University, Erandawane, Pune 411038, India
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  • MANDA Lemos,

    1. Centro de Engenharia Biológica e Química, Instituto Superior Técnico, Departamento de Engenharia Química, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
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  • Francisco Lemos,

    1. Centro de Engenharia Biológica e Química, Instituto Superior Técnico, Departamento de Engenharia Química, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
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  • Maria M. Marques

    Corresponding author
    1. Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
    • Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
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Abstract

In this article, the experimental results obtained in the copolymerization of ethylene with polar monomers using a silylated α-diimine nickel catalyst are described and compared with those obtained with a non-silylate similar one. The results show that the introduction of a siliyl group in the para-position of the imine moiety turns the catalyst less sensitive toward polar functionalities. However, the reactivity observed in copolymerization reactions was found to be reduced both the global polymerization and incorporation rates. Molecular modeling calculation allowed us to understand both the preferred insertion mode and the intermediate product structures for E/MMA copolymerization. Photodegradation studies showed that the presence of polar groups in the copolymers increases their rate of oxidation and turn them more easily degradable. The stabilization performed by Tinuvin 770 showed that for long-exposure times, it is not very effective regardless it is only mixed or grafted to the copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

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