Abstract
Formation of nanostructures inside epoxy thermosets by the inclusion of appropriate block copolymers (BCPs) has been emerged as a promising approach to optimize epoxy thermoset material properties for potential applications. For the last two decades, tremendous efforts have been made by researchers to create ordered or disordered nanostructures in epoxy thermosets by the incorporation of reactive or nonreactive BCPs in an attempt to develop toughened thermosets suitable for specific applications. This chapter briefly reviews the different mechanisms of phase separation in epoxy/BCP systems, such as self-assembly and reaction-induced microphase separation (RIMPS), and outlines some of the important features of nanostructured morphologies and their influence on fracture toughness of fabricated products.
References
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
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
Dean JM, Verghese NE, Pham HQ, Bates FS (2003) Nanostructure toughened epoxy resins. Macromolecules 36:9267–9270
Fan W, Zheng S (2008) Reaction-induced microphase separation in thermosetting blends of epoxy resin with poly(methyl methacrylate)-block-polystyrene block copolymers: effect of topologies of block copolymers on morphological structures. Polymer 49:3157–3167
Fan W, Wang L, Zheng S (2009) Nanostructures in thermosetting blends of epoxy resin with polydimethylsiloxane-block-poly(ε-caprolactone)-block-polystyrene ABC triblock copolymer. Macromolecules 42:327–336
Fan W, Wang L, Zheng S (2010) Double reaction-induced microphase separation in epoxy resin containing polystyrene-block-poly(ε-caprolactone)-block-poly-(n-butyl acrylate) ABC triblock copolymer. Macromolecules 43:10600–10611
Garate H, Mondragon I, Goyanes S, D’Accorso NB (2011) Controlled epoxidation of poly(styrene-b-isoprene-b-styrene) block copolymer for the development of nanostructure epoxy thermosets. J Polym Sci Part A Polym Chem 49:4505–4513
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
Garate H, Goyanes S, D’Accorso NB (2014) Controlling nanodomain morphology of epoxy thermosets modified with reactive amine-containing epoxidized poly(styrene-b-isoprene-b-styrene) block copolymer. Macromolecules 47:7416–7423
George SM, Puglia D, Kenny JM, Parameswaranpillai J, Vijayan P, Pionteck J, Thomas S (2015) Volume shrinkage and rheological studies of epoxidised and unepoxidised poly(styrene-block-butadiene-block-styrene) triblock copolymer modified epoxy resin-diamino diphenyl methane nanostructured blend systems. Phys Chem Chem Phys 17:12760–12770
Girard-Reydet E, Sevignon A, Pascault JP, Hoppe CE, Galante MJ, Oyanguren PA, Williams RJJ (2002) Influence of the addition of polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) on the morphologies generated by reaction-induced phase separation in PS/PMMA/epoxy blends. Macromol Chem Phys 203:947–952
Epoxy Resins Market – Global Industry Analysis, Size, Share, Growth, Trends and Forecast, 2014–2020. http://www.transparencymarketresearch.com/epoxy-resins-market.html
Gong W, Zeng K, Wang L, Zheng S (2008) Poly(hydroxyether of bisphenol A)-block-polydimethylsiloxane alternating block copolymer and its nanostructured blends with epoxy resin. Polymer 49:3318–3326
Guo Q, Dean JM, Grubbs RB, Bates FS (2003) Block copolymer modified novolac epoxy resin. J Polym Sci Part B Polym Phys 41:1994–2003
Guo Q, Chen F, Wang K, Chen L (2006a) Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)-block-poly(dimethylsiloxane) diblock copolymer. J Polym Sci Part B Polym Phys 44:3042–3052
Guo Q, Wang K, Chen L, Zheng S, Halley PJ (2006b) Phase behavior, crystallization, and nanostructures in thermoset blends of epoxy resin and amphiphilic star-shaped block copolymers. J Polym Sci Part B: Polym Phys 44:975–985
Guo Q, Liu J, Chen L, Wang K (2008) Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic polyisoprene-block-poly(4-vinyl pyridine) reactive diblock copolymer. Polymer 49:1737–1742
He X, Liu Y, Zhang R, Wu Q, Chen T, Sun P, Wang X, Xue G (2014) Unique interphase and cross-linked network controlled by different miscible blocks in nanostructured epoxy/block copolymer blends characterized by solid-state NMR. J Phys Chem C 118:13285–13299
Heng Z, Chen Y, Zou H, Liang M (2015) Simultaneously enhanced tensile strength and fracture toughness of epoxy resins by a poly(ethylene oxide)-block-carboxyl terminated butadiene-acrylonitrile rubber dilock copolymer. RSC Adv 5:42362–42368
Hillmyer MA, Lipic PM, Hajduk DA, Almdal K, Bates FS (1997) Self-assembly and polymerization of epoxy resin-amphiphilic block copolymer nanocomposites. J Am Chem Soc 119:2749–2750
Hu D, Zheng S (2009) Reaction-induced microphase separation in epoxy resin containing polystyrene-block-poly(ethylene oxide) alternating multiblock copolymer. Eur Polym J 45:3326–3338
Hu D, Zhang C, Yu R, Wang L, Zheng S (2010) Self-organized thermosets involving epoxy and poly(ε-caprolactone)-block-poly(ethylene-co-ethylethylene)-block-poly(ε-caprolactone) amphiphilic triblock copolymer. Polymer 51:6047–6057
Kishi H, Kunimitsu Y, Imade J, Oshita S, Morishita Y, Asada M (2011) Nano-phase structures and mechanical properties of epoxy/acryl triblock copolymer alloys. Polymer 52:760–768
Leonardi AB, Zucchi IA, Williams RJJ (2015) Generation of large and locally aligned wormlike micelles in block copolymer/epoxy blends. Eur Polym J 65:202–208
Lipic PM, Bates FS, Hillmyer MA (1998) Nanostructured thermosets from self-assembled amphiphilic block copolymer/epoxy resin mixtures. J Am Chem Soc 120:8963–8970
Liu J, Sue H, Thompson ZJ, Bates FS, Dettloff M, Jacob G, Verghese N, Pham H (2008) Nanocavitation in self-assembled amphiphilic block copolymer-modified epoxy. Macromolecules 41:7616–7624
Liu J, Thompson ZJ, Sue H, Bates FS, Hillmyer MA, Dettloff M, Jacob G, Verghese N, Ha P (2010) Toughening of epoxies with block copolymer micelles of wormlike morphology. Macromolecules 43:7238–7243
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
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
Meng F, Xu Z, Zheng S (2008) Microphase separation in thermosetting blends of epoxy resin and poly(ε-caprolactone)-block-polystyrene block copolymers. Macromolecules 41:1411–1420
Mijovic J, Shen M, Sy JW, Mondragon I (2000) Dynamics and morphology in nanostructured thermoset network/block copolymer blends during network formation. Macromolecules 33:5235–5244
Ocando C, Serrano E, Tercjak A, Pena 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
Ocando C, Fernández R, Tercjak A, Mondragon I, Eceiza A (2013) Nanostructured thermoplastic elastomers based on SBS triblock copolymer stiffening with low contents of epoxy system. Morphological behavior and mechanical properties. Macromolecules 46:3444–3451
Parameswaranpillai J, Sidhardhan SK, Jose S, Siengchin S, Pionteck J, Magueresse A, Grohens Y, Hameed N (2017) Reaction-induced phase separation and resulting thermomechanical and surface properties of epoxy resin/poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) blends cured with 4,4′-diaminodiphenylsulfone. J Appl Polym Sci 134:44406
Pascault JP, Williams RJJ (2010) General concepts about epoxy polymers. In: Pascault J-P, Williams RJJ (eds) Epoxy polymers: new materials and innovations. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. doi:10.1002/9783527628704.ch1
Ramos JA, Espósito LH, Fernández R, Zalakain I, Goyanes S, Avgeropoulos A, Zafeiropoulos NE, Kortaberria G, Mondragon I (2012) Block copolymer concentration gradient and solvent effects on nanostructuring of thin epoxy coatings modified with epoxidized styrene−butadiene−styrene block copolymers. Macromolecules 45:1483–1491
Redline EM, Declet-Perez C, Bates FS, Francis LF (2014) Effect of block copolymer concentration and core composition on toughening epoxies. Polymer 55:4172–4181
Ritzenthaler S, Court F, David L, Girard-Reydet E, Leibler L, Pascault JP (2002) ABC triblock copolymers/epoxy-diamine blends. 1. Keys to achieve nanostructured thermosets. Macromolecules 35:6245–6254
Ritzenthaler S, Court F, Girard-Reydet E, Leibler L, Pascault JP (2003) ABC triblock copolymers/epoxy-diamine blends. 2. Parameters controlling the morphologies and properties. Macromolecules 36:118–126
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
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
Serrano E, Kortaberria G, Arruti P, Tercjak A, Mondragon I (2009) Molecular dynamics of an epoxy resin modified with an epoxidized poly(styrene–butadiene) linear block copolymer during cure and microphase separation processes. Eur Polym J 45:1046–1057
Thio YS, Wu J, Bates FS (2006) Epoxy toughening using low molecular weight poly(hexylene oxide)-poly(ethylene oxide) diblock copolymers. Macromolecules 39:7187–7189
Thompson ZJ, Hillmyer MA, Liu J, Sue H, Dettloff M, Bates FS (2009) Block copolymer toughened epoxy: role of cross-link density. Macromolecules 42:2333–2335
Wu S, Guo Q, Peng S, Hameed N, Kraska M, Stühn B, Mai Y (2012) Toughening epoxy thermosets with block ionomer complexes: a nanostructure−mechanical property correlation. Macromolecules 45:3829–3840
Xu Z, Zheng S (2007a) Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly(ε-caprolactone)-bock-polydimethylsiloxane-block-poly(ε-caprolactone) triblock copolymer. Polymer 48:6134–6144
Xu Z, Zheng S (2007b) Reaction-induced microphase separation in epoxy thermosets containing poly(ε-caprolactone)-block-poly(n-butyl acrylate) diblock copolymer. Macromolecules 40:2548–2558
Yang X, Yi F, Xin Z, Zheng S (2009) Morphology and mechanical properties of nanostructured blends of epoxy resin with poly(ε-caprolactone)-block-poly(butadiene-co-acrylonitrile)-block-poly(ε-caprolactone) triblock copolymer. Polymer 50:4089–4100
Yi F, Zheng S, Liu T (2009) Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer. J Phys Chem B 113:1857–1868
Yi F, Yu R, Zheng S, Li X (2011) Nanostructured thermosets from epoxy and poly(2,2,2-trifluoroethyl acrylate)-block-poly(glycidyl methacrylate) diblock copolymer: demixing of reactive blocks and thermomechanical properties. Polymer 52:5669–5680
Yu R, Zheng S (2011) Morphological transition from spherical to lamellar nanophases in epoxy thermosets containing poly(ethylene oxide)-block-poly(ε-caprolactone)-block-polystyrene triblock copolymer by hardeners. Macromolecules 44:8546–8557
Yu R, Zheng S, Li X, Wang J (2012) Reaction-induced microphase separation in epoxy thermosets containing block copolymers composed of polystyrene and poly(ε-caprolactone): influence of copolymer architectures on formation of nanophases. Macromolecules 45:9155–9168
Zhang C, Li L, Zheng S (2013) Formation and confined crystallization of polyethylene nanophases in epoxy thermosets. Macromolecules 46:2740–2753
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer International Publishing AG
About this entry
Cite this entry
Jose, S., George, S.M., Parameswaranpillai, J. (2016). Introduction to 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_29-1
Download citation
DOI: https://doi.org/10.1007/978-3-319-18158-5_29-1
Received:
Accepted:
Published:
Publisher Name: Springer, Cham
Online ISBN: 978-3-319-18158-5
eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics