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Morphology of Epoxy/Block Copolymer Blends

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Handbook of Epoxy Blends

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Abstract

The ability of block copolymers to generate nanostructures when mixed with epoxy thermosetting systems is deeply analyzed. Both amphiphilic and chemically modified di- or triblock copolymers have been used with this purpose. In both cases, one of the blocks is miscible with epoxy system (or even can react with it) before and after curing, while the other one is immiscible before or after curing, leading to morphology development by self-assembly (SA) or reaction-induced phase separation (RIPS), respectively. In some cases, nanostructure development can occur by a combination of both mechanisms or even some demixing of the miscible block can also happen, generating different morphologies. Depending on that and on other parameters like employed hardener, cure cycle, copolymer block ratio, and topology among others, different morphologies such as spherical or wormlike micelles, hexagonally packed cylinders, bilayer micelles, or mixtures of them can be obtained. The effect of nanofillers on morphologies of ternary systems based on epoxy systems nanostructured with block copolymers is also analyzed.

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References

  • Bashar MT, Sundaraj U, Mertiny P (2014) Morphology and mechanical properties of nanostructured acrylic tniblock copolymer modified epoxy. Polym Eng Sci 54:1047–1055

    Article  CAS  Google Scholar 

  • Blanco M, Lopez M, Kortaberria G, Mondragon I (2010) Nanostructured thermosets from self-assembled amphiphilic block copolymer/epoxy resin mixtures: effect of copolymer content on nanostructures. Polym Int 59:523–528

    Article  CAS  Google Scholar 

  • Cano L, Builes DH, Tercjak A (2014) Morphological and mechanical study of nanostructured epoxy systems modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer. Polymer 55:738–745

    Article  CAS  Google Scholar 

  • Casaban L, Kirsten M, Pegel S, Carrasco PM, Garcia I, Stamm M, Kenny JM (2013) Shear induced orientation of phase-segregated copolymer/epoxy blends. Eur Polym J 49:3359–3365

    Article  CAS  Google Scholar 

  • Cong H, Zheng S (2014) Formation of nanostructures in thermosets containing block copolymers: from self-assembly to reaction-induced microphase separation mechanism. Polymer 55:1190–1201

    Article  CAS  Google Scholar 

  • Esposito LH, Ramos JA, Mondragon I, Kortaberria G (2013) Nanostructured thermosetting epoxy systems modified with poly(isoprene-b-methyl methacrylate) diblock copolymer and polyisoprene-grafted carbon nanotubes. J Appl Polym Sci 129:1060–1067

    Article  CAS  Google Scholar 

  • Esposito LH, Ramos JA, Kortaberria G (2014) Dispersion of carbon nanotubes in nanostructured epoxy systems for coating application. Prog Org Coat 77:1452–1458

    Article  CAS  Google Scholar 

  • Fan W, Zheng S (2008) Reaction induced microphase separation in thermosetting blends of epoxy resin with poly(methylmethacrylate)-block-poly(styrene) block copolymers: effect of topology of block copolymer on morphological structures. Polymer 49:3157–3167

    Article  CAS  Google Scholar 

  • Fan W, Wang L, Zheng S (2009) Nanostructures in thermosetting blends of epoxy resin with polydimethylsiloxane-block-poly (ε-caprolactone)-block-polystrene ABC tniblock copolymer. Macromolecules 42:327–336

    Article  CAS  Google Scholar 

  • Francis R, Baby DK (2014) Toughening of epoxy thermoset with polystyrene-b-polyglycolic acid star copolymer: nanostructure-mechanical property correlation. Ind Eng Chem Res 53:19945–19951

    Article  Google Scholar 

  • Garate H, Mondragon I, Goyanes S, D’Accorso N (2011) Controlled epoxidation of poly(styrene-b-isoprene-b-styrene) block copolymer for the development of nanostructured epoxy thermosets. J Polym Sci A Polym Chem 49:4505–4513

    Article  CAS  Google Scholar 

  • Garate H, Mondragon I, D’Accorso NB, Goyanes S (2013) Exploring microphase separation behavior of epoxidized poly(styrene-b-isoprene-b-styrene) block copolymer inside thin epoxy coatings. Macromolecules 46:2182–2187

    Article  CAS  Google Scholar 

  • Garate H, Goyanes S, D’Accorso N (2014) Controlling nanodomain morphology of epoxy thermosets modified with reactive amine-containing epoxidized poly(styrene-b-isoprene-b-styrene) triblock copolymer. Macromolecules 47:7416–7423

    Article  CAS  Google Scholar 

  • George SN, Puglia D, Kenny JM, Jyotishkumar P, Thomas S (2012) Cure kinetics and thermal stability of micro and nanostructured thermosetting blends of epoxy resin and epoxidized styrene-block-butadiene-block-styrene triblock copolymer systems. Polym Eng Sci 52:2336–2347

    Article  CAS  Google Scholar 

  • George SN, Puglia D, Kenny JM, Causin V, Jyotishkumar P, Thomas S (2013) Morphological and mechanical characterization of nanostructured thermosets from epoxy and styrene-block-butadiene-block-styrene triblock copolymer. Ind Eng Chem Res 52:9121–9129

    Article  CAS  Google Scholar 

  • Grubbs RB, Dean JM, Broz ME, Bates FS (2000a) Reactive block copolymers for modification of thermosetting epoxy. Macromolecules 33:9522–9534

    Article  CAS  Google Scholar 

  • Grubbs RB, Dean JM, Broz ME, Bates FS (2000b) Selectively epoxidized polyisoprene-b-polybutadiene block copolymers. Macromolecules 33:2308–2310

    Article  CAS  Google Scholar 

  • Guo Q, Thomann R, Gronski W (2002) Phase behavior, crystallization and hierarchial nanostructures in self organised thermoset blends of epoxy resin and amphiphilic poly (ethylene oxide) -block-poly (propylene oxide) -block- poly (ethylene oxide) tniblock copolymers. Macromolecules 35:3133–3144

    Article  CAS  Google Scholar 

  • Guo Q, Wang K, Chen L, Zheng S, Halley PJ (2006) Phase behavior, crystallization and nanostructures in thermoset blends of epoxy resin with amphiphilic star-shaped block copolymers. J Polym Sci B Polym Phys 44:975–985

    Article  CAS  Google Scholar 

  • Guo Q, Liu J, Chen N, Wang K (2008) Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic poly(isoprene)-b-poly(4-vinyl pyridine) reactive block copolymer. Polymer 49:1737–1742

    Article  CAS  Google Scholar 

  • Gutierrez J, Tercjak A, Mondragon I (2010a) Transparent nanostructured thermoset composites containing well-dispersed TiO2 nanoparticles. J Phys Chem C 114:22424–22430

    Article  CAS  Google Scholar 

  • Gutierrez J, Tercjak A, Mondragon I (2010b) Conductive behavior of high TiO2 nanoparticle content of inorganic/organic nanostructured composites. J Am Chem Soc 132:873–878

    Article  CAS  Google Scholar 

  • Gutierrez J, Mondragon I, Tercjak A (2011) Morphological and optical behavior of thermoset matrix composites varying both polystyrene-block-poly(ethylene oxide) and TiO2 nanoparticle content. Polymer 52:5699–5707

    Article  CAS  Google Scholar 

  • Hameed N, Guo Q, Xu Z, Hanley TL, Mai YW (2010) Reactive block copolymer modified thermosets: highly ordered nanostructures and improved properties. Soft Matter 6:6119–6129

    Article  CAS  Google Scholar 

  • Hillmyer MA, Lipic PM, Hadjuk DA, Almdal K, Bater F (1997) Self assembly and polymerization of epoxy resin-amphiphilic block copolymer nanocomposites. J Am Chem Soc 119:2749–2750

    Article  CAS  Google Scholar 

  • Hu D, Zhang C, Yu R, Wang L, Zheng S (2010) Self-organized thermosets involving epoxy/poly(ε-caprolactone)-b-poly(ethylene-co-ethylethylene)-b-poly(ε-caprolactone) amphiphilic triblock copolymer. Polymer 51:6047–6057

    Article  CAS  Google Scholar 

  • Johnsen BB, Kinloch AJ, Mohammed RD, Taylor AC, Sprenger S (2007) Toughening mechanisms of nanoparticle-modified epoxy polymers. Polymer 48:530–541

    Article  CAS  Google Scholar 

  • Larrañaga M, Gabilondo N, Kortaberria G, Serrano E, Remiro P, Riccardi CC, Mondragon I (2005) Micro- or nanoseparated phases in thermoset blends of an epoxy resin and PEO-PPO-PEO triblock copolymer. Polymer 18:7082–7093

    Article  Google Scholar 

  • Larrañaga M, Serrano E, Martin MD, Tercjak A, Kortaberria G, De la Caba K, Mondragon I (2007) Miscibility and mechanical properties of an amine-cured epoxy resin blended with block copolymer. Polym Int 56:1392–1403

    Article  Google Scholar 

  • Lipic PM, Bates FS, Hillmyer MA (1998) Nanostructured thermosets from self-assembled block copolymer/epoxy resin mixtures. J Am Chem Soc 120:8963–8970

    Article  CAS  Google Scholar 

  • Liu JD, Sue HJ, Thompson ZJ, Bates FS, Dettloff M, Jacob G (2008) Nanocavitation in self-assembled amphiphilic block copolymer-modified epoxy. Macromolecules 41:7616–7624

    Article  CAS  Google Scholar 

  • Meng F, Zheng S, Li H, Liang Q, Liu T (2006a) Formation of ordered nanostructures in epoxy thermosets: a mechanism of reaction-induced microphase separation. Macromolecules 39:5072–5080

    Article  CAS  Google Scholar 

  • Meng F, Zheng S, Liu T (2006b) Epoxy resin containing poly(ethylene oxide)-block-poly(ε-caprolactone) diblock copolymer: effect of curing agents on nanostructures. Polymer 47:7590–7600

    Article  CAS  Google Scholar 

  • Meng F, Zheng S, Zhang W, Li H, Liang Q (2006c) Nanostructured thermosetting blends of epoxy resin and amphiphilic poly(ε-caprolactone)-block-polybutadiene-block-poly(ε-caprolactone) triblock copolymer. Macromolecules 39:711–719

    Article  CAS  Google Scholar 

  • Meng F, Xu Z, Zheng S (2008) Microphase separation in thermosetting blends of epoxy resin and poly(ε-caprolactone)-block-poly(styrene) block copolymers. Macromolecules 41:1411–1420

    Article  CAS  Google Scholar 

  • Ocando C, Serrano E, Tercjak A, Peña C, Kortaberria G, Calberg C, Grignard B, Jerome R, Carrasco PM, Mecerreyes D, Mondragon I (2007) Structure and properties of a semifluorinated diblock copolymer modified epoxy blend. Macromolecules 40:4068–4074

    Article  CAS  Google Scholar 

  • Ocando C, Tercjak A, Martin MD, Ramos JA, Campo M, Mondragon I (2008a) Morphology development in thermosetting mixtures through the variation of chemical functionalization degree of poly(styrene-block-butadiene) diblock copolymer modifiers. Thermomecanical properties. Macromolecules 42:6215–6224

    Article  Google Scholar 

  • Ocando C, Tercjak A, Martin MD, Ramos JA, Corona-Galvan S, Perellada MD, Mondragon I (2008b) Micro- and macrophase separation of thermosetting systems modified with epoxidized poly(styrene-block-butadiene-block-styrene) linear triblock copolymers and their influence on final mechanical properties. Polym Int 57:1333–1342

    Article  CAS  Google Scholar 

  • Ocando C, Tercjak A, Martin MD, Ramos JA, Campo M, Mondragon I (2009) Morphology development in thermosetting mixtures through the variation on chemical functionalization degree of SB diblock copolymer modifiers. Thermomechanical properties. Macromolecules 42:6215–6224

    Article  CAS  Google Scholar 

  • Ocando C, Tercjak A, Mondragon I (2010) Nanostructured systems based on SBS epoxidized triblock copolymers and well-dispersed alumina/epoxy matrix composites. Compos Sci Technol 70:1106–1112

    Article  CAS  Google Scholar 

  • Pethrick RA, Miller C, Rhoney I (2010) Influence of nanosilica particles on the cure and physical properties of an epoxy thermoset resin. Polym Int 59:236–241

    CAS  Google Scholar 

  • Rebizant V, Abetz V, Tournillac F, Leibler L (2003) Reactive block copolymers containing glycidyl methacrylate. Synthesis and morphology control in epoxy-amine networks. Macromolecules 36:9889–9896

    Article  CAS  Google Scholar 

  • Rebizant V, Venet AS, Tournillac F, Girard-Reydet E, Navarro C, Pascault JP, Leibler L (2004) Chemistry and mechanical properties of epoxy-based thermosets reinforced by reactive and non-reactive SBMX block copolymers. Macromolecules 37:8017–8027

    Article  CAS  Google Scholar 

  • Ritzenthaler S, Court F, David L, Girard-Reydet E, Leibler L, Pascault JP (2002) ABC triblock copolymer/epoxy diamine blends. 1. Keys to achieve nanostructured thermosets. Macromolecules 35:6245–6254

    Article  CAS  Google Scholar 

  • Romeo HE, Zucchi IA, Rico M, Hoppe CE, Williams RJJ (2013) From spherical micelles to hexagonally packed cylinders: the cure cycle determines nanostructures generated in block copolymer/epoxy blends. Macromolecules 46:4854–4861

    Article  CAS  Google Scholar 

  • Serrano E, Larrañaga M, Kortaberria G, Remiro PM, Mondragon I (2005a) Towards nanostructured materials by modification of thermosetting matrices with block copolymers. In: Zaikov GE, Jimenez A (eds) New developments in polymer analysis, stabilization and degradation. Nova Science, Moscow, pp 45–55

    Google Scholar 

  • Serrano E, Martin MD, Tercjak A, Pomposo J, Mecerreyes D, Mondragon I (2005b) Nanostructured thermosetting systems from epoxidized styrene butadiene block copolymers. Macromol Rapid Commun 26:982–985

    Article  CAS  Google Scholar 

  • Serrano E, Tercjak A, Kortaberria G, Pomposo JA, Mecerreyes D, Zafeiropoulos NE, Stamm M, Mondragon I (2006) Nanostructured thermosetting systems by modification with epoxidized styrene-butadiene star block copolymers. Effect of epoxidation degree. Macromolecules 39:2254–2261

    Article  CAS  Google Scholar 

  • Serrano E, Tercjak A, Ocando C, Larrañaga M, Perellada MD, Corona-Galvan S, Mecerreyes D, Zafeiropoulos NE, Stamm M, Mondragon I (2007) Curing behavior and final properties of nanostructured thermosetting systems modified with epoxidized styrene butadiene linear diblock copolymers. Macromol Chem Phys 208:2281–2292

    Article  CAS  Google Scholar 

  • Sinturel C, Vayer M, Erre R, Amenitsch H (2007) Nanostructured polymers obtained from polyethylene-b-poly(ethylene oxide) block copolymer in unsaturated polyester. Macromolecules 40:2532–2538

    Article  CAS  Google Scholar 

  • Tercjak A, Mondragon I (2008) Relationships between the morphology and thermoresponsive behavior in micro/nanostructured thermosetting matrixes containing a 4′-(hexyloxy)-4-biphenylcarbonitrile liquid crystal. Langmuir 24:11216–11224

    Article  CAS  Google Scholar 

  • Tercjak A, Mondragon I (2010) Polymer dispersed liquid crystal, thermotropic and other responsive epoxy polymers. In. Pascault JP (ed) Epoxy polymers, Wiley, Berlin, pp 124–136

    Google Scholar 

  • Tercjak A, Gutierrez J, Peponi L, Rueda L, Mondragon I (2009) Arrangement of conductive TiO2 nanoparticles in hybrid inorganic/organic thermosetting materials using liquid crystal. Macromolecules 42:3386–3390

    Article  CAS  Google Scholar 

  • Tercjak A, Gutierrez J, Martin MD, Mondragon I (2012) Transparent titanium dioxide/block copolymer modified epoxy-based systems in the long-scale microphase separation threshold. Eur Polym J 48:16–25

    Article  CAS  Google Scholar 

  • Thio YS, Wu J, Bates FS (2006) Structure and properties of PBO-b-PEO diblock copolymer modified epoxy. J Polym Sci B Polym Phys 43:1950–1965

    Google Scholar 

  • Wang L, Zhang C, Cong H, Li L, Zheng S (2013) Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies. J Phys Chem B 117:8256–8268

    Article  CAS  Google Scholar 

  • Xu Z, Zheng S (2007) Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly (ε-caprolactone)-block-(polydimethyl siloxane)-block-poly(ε-caprolactone) tniblock copolymer. Polymer 48:6134–6144

    Article  CAS  Google Scholar 

  • Yang X, Yi F, Xin Z, Zheng S (2009) Morphology and mechanical properties of nanostructured blends of epoxy resin with poly(ε-caprolactone)-b-poly(butadiene-co-acrylonitrile)-b-poly(i;-caprolactone) triblock copolymer. Polymer 50:4089–4100

    Google Scholar 

  • Yi F, Zheng S (2009) Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-b-poly(ethylene oxide) amphiphilic diblock copolymer. J Phys Chem B 113:1857–1868

    Article  CAS  Google Scholar 

  • Yi F, Yu R, Zheng S, Li X (2011) Nanostructured thermosets from epoxy and poly(2,2,2-trifluoroethyl acrylate)-b-poly(glycidyl methacrylate) diblock copolymer: demixing of reactive blocs and thermomechanical properties. Polymer 52:5669–5680

    Article  CAS  Google Scholar 

  • Yu R, Zheng S (2011) Morphological transition from spherical to lamellar nanophases in epoxy thermosets containing poly(ethylene oxide)-b-poly(ε-caprolactone)-b-poly(styrene) triblock copolymer by hardeners. Macromolecules 44:8546–8557

    Article  CAS  Google Scholar 

  • Zhang Ċ, Zheng S (2013) Formation and confined crystallization of polyethylene nanophases in epoxy thermosets. Macromolecules 46:2740–2753

    Article  CAS  Google Scholar 

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Acknowledgments

Financial support from the Basque Country Government (Grupos Consolidados, IT-776-13) and the Ministry of Economy and Competitiveness – Spain (MAT MAT2015-66149-P) is gratefully acknowledged.

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Authors and Affiliations

  1. “Materials + Technologies” Group, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, Plaza Europa 1, 20018, Donostia, Spain

    Galder Kortaberria

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  1. Galder Kortaberria
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Correspondence to Galder Kortaberria .

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Editors and Affiliations

  1. Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi, India

    Jyotishkumar Parameswaranpillai

  2. Institute for Frontier Materials, Deakin University, Geelong, Victoria, Australia

    Nishar Hameed

  3. Leibniz-Institut für Polymerforschung , Dresden, Germany

    Jürgen Pionteck

  4. Department of Chemical Engineering, National Cheng Kung University, Taiwan, China

    Eamor M. Woo

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Kortaberria, G. (2016). Morphology of Epoxy/Block Copolymer Blends. In: Parameswaranpillai, J., Hameed, N., Pionteck, J., Woo, E. (eds) Handbook of Epoxy Blends. Springer, Cham. https://doi.org/10.1007/978-3-319-18158-5_32-2

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  • DOI: https://doi.org/10.1007/978-3-319-18158-5_32-2

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  • Online ISBN: 978-3-319-18158-5

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Chapter history

  1. Latest

    Morphology of Epoxy/Block Copolymer Blends
    Published:
    22 March 2016

    DOI: https://doi.org/10.1007/978-3-319-18158-5_32-2

  2. Original

    Morphology of Epoxy/Block Copolymer Blends
    Published:
    30 January 2016

    DOI: https://doi.org/10.1007/978-3-319-18158-5_32-1

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