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Controlled epoxidation of poly(styrene-b-isoprene-b-styrene) block copolymer for the development of nanostructured epoxy thermosets

Authors

  • Hernan Garate,

    1. CIHIDECAR-CONICET, Dpto Química Orgánica, FCEyN-UBA, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina
    2. IFIBA-CONICET, LP&MC, Dpto Física, FCEyN-UBA, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina
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  • Iñaki Mondragon,

    1. Dpto Ingeniería Química y Medio Ambiente, Escuela Politécnica, University of the Basque Country, Pza. Europa 1, 20018 Donostia-San Sebastián, Spain
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  • Silvia Goyanes,

    1. IFIBA-CONICET, LP&MC, Dpto Física, FCEyN-UBA, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina
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  • Norma B. D'Accorso

    Corresponding author
    1. CIHIDECAR-CONICET, Dpto Química Orgánica, FCEyN-UBA, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina
    • CIHIDECAR-CONICET, Dpto Química Orgánica, FCEyN-UBA, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina
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Abstract

To be used as templates for nanostructured thermosets, a commercial poly(styrene-b-isoprene-b-styrene) (SIS) block copolymer (BCP) was epoxidized by three different epoxidation procedures. An exhaustive analysis of methodologies using metal catalyzed/hydrogen peroxide, dimethyldioxirane (DMDO), and meta-chloroperbenzoic acid (m-CPBA) was performed to obtain reactive BCPs. The DMDO approach was the best strategy to obtain highly epoxidized SIS BCP (85 mol %) without formation of side products. Careful control in BCP epoxidation by metal catalyzed/hydrogen peroxide and m-CPBA approaches led to a maximum epoxidation degree (ED) of approximately 60 mol % without the formation of side products. The ED by metal catalyzed/hydrogen peroxide strategy could be further increased to 69 mol %, but a significant amount of crosslinking, ring opening, and polymer chain scission reactions were detected by spectroscopic and chromatographic techniques. The miscibility of epoxidized BCPs with diglycidyl ether of bisphenol-A epoxy system before and after curing was analyzed to develop nanostructured epoxy thermosets. For ED higher than 69 mol %, BCPs were miscible, while those with lower ED presented macrophase separation. Highly epoxidized BCPs obtained by the DMDO methodology were successfully used to obtain ordered nanodomains inside the epoxy matrix, as determined by atomic force microscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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