Poly(methyl methacrylate)-b-poly (n-butyl acrylate)-b-poly(ε-caprolactone) triblock copolymers as tougheners for PMMA matrices

Nelly Chagneux, Jules Kierkels, Thierry Leblanc, Thomas Trimaille, Han Meijer, Pierre Gérard, Didier Gigmes, Denis Bertin, Han Goossens

Research output: Chapter in Book/Report/Conference proceedingChapterAcademicpeer-review


Poly(methyl methacrylate)-b-poly(butyl acrylate)-b-poly(ε-capro-lactone) (PMMA-PBA-PCL) triblock copolymers of typical number-averaged block molecular weights of 45 to 100 kg/mol for PMMA, 25 kg/mol for PBA and 10 kg/mol for PCL were synthesized by sequential nitroxide-mediated polymerization (NMP) of BA and MMA from a SG1 (N-(tert-butyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)) nitroxide-functionalized PCL macroalkoxyamine initiator. This alkoxy-amine was obtained by transformation of an OH-terminated PCL into acrylate-end capped PCL, followed by 1,2-intermolecular radical addition (IRA) of MAMA-SG1 (so-called BlocBuilder® MA). NMP of BA from the macroalkoxyamine proceeded in a controlled manner. The high living chain ratio of PBA-PCL allowed further initiation of NMP of MMA, leading to triblock copolymers with adjustable PMMA block molecular weights. The samples prepared by solvent casting were found to organize in a lamellar morphology for the pure triblock copolymers, and in a spherical morphology when blended with a PMMA homo-polymer of Mn = 40 kg/mol and polydispersity index of 2.1. Finally, the mechanical properties and the local deformation mechanisms of the pure triblock copolymers and their blends with PMMA were investigated by time-resolved SAXS measurements during tensile testing. The dominant microscopic deformation mode of the triblock copolymer was found to change from crazing to cavitation-induced shear yielding, due to the easy-cavitating PCL block of the copolymer.

Original languageEnglish
Title of host publicationBlock Copolymers
Subtitle of host publicationPhase Morphology, Material Applications and Future Challenges
Place of PublicationNew York
PublisherNova Science
Number of pages19
ISBN (Electronic)9781629486260
ISBN (Print)9781629486253
Publication statusPublished - 1 Jan 2014


  • Block copolymers
  • Deformation mechanisms
  • Nitroxide-mediated polymerization
  • Toughness


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