Micromechanics of “raspberry” morphology in PPE/SAN polymer blends compatibilized with linear ABC triblock terpolymers
Abstract The effect of compatibilization with a symmetrical polystyrene- block -polybutadiene- block -poly(methyl methacrylate) (SBM) triblock terpolymer on the morphological and mechanical properties (specifically toughness) of immiscible poly(2,6-dimethyl-1,4-phenylene ether)/poly(styrene- co -acrylonitrile) (PPE/SAN) blends with different blend (w/w) ratios is investigated. We study the effect of blend viscosity on the localization of the compatibilizer at the blend interface, influencing the mechanical properties of the macroscopic material. The impact of the specific morphology of the blends, known as “raspberry morphology”, on the final material will be explained using thermomechanica…
Guided hierarchical co-assembly of soft patchy nanoparticles.
Different polymers can be used in combination to produce coexisting nanoparticles of different symmetry and tailored to co-assemble into well-ordered binary and ternary hierarchical structures. There is considerable practical interest in developing the tools to fabricate multicomponent artificial systems that mimic the hierarchical ordering seen in the natural world — complex biomaterials can be assembled from the simple but precisely defined molecular building blocks. Andre Groschel and colleagues have developed a bottom-up approach that's a step in that direction. Previously they designed simple linear polymers that self-assemble in solution to produce monodisperse nanoparticles with well…
“Dumb” pH-Independent and Biocompatible Hydrogels Formed by Copolymers of Long-Chain Alkyl Glycidyl Ethers and Ethylene Oxide
The formation and rheological properties of hydrogels based on amphiphilic ABA triblock polyether copolymers are described, relying solely on the hydrophobic interaction of long-chain alkyl glycidyl ether (AlkGE)- based A-blocks that are combined with a hydrophilic poly(ethylene glycol) (PEG) midblock. Via anionic ring-opening copolymerization (AROP), ethylene oxide (EO) and long-chain alkyl glycidyl ethers (AlkGEs) were copolymerized, using deprotonated poly(ethylene glycol) (PEG) macroinitiators (Mn of 10, 20 kg mol-1). The polymerization afforded amphiphilic ABA triblock copolymers with molar masses in the range of 21-32 kg mol-1 and dispersities (Đ) of Đ = 1.07-1.17. Kinetic studies rev…
Crystallization-induced switching of the morphology of poly(ethylene oxide)-block-polybutadiene micelles
We studied the morphology of micelles formed by a well-defined poly(1,2-butadiene)-block-poly(ethylene oxide) diblock copolymer (PB-b-PEO). Dissolved in n-heptane at 70 °C, that is, above the melting point of PEO, spherical micelles are formed due to the selectivity of the solvent for the PB-block. If the solutions are cooled down to low temperatures, the liquid PEO-block crystallizes within the cores of the spherical micelles that remain stable. If, however, the solutions are quenched to 30 °C, the spherical micelles aggregate to a novel meander-like structure within several minutes. In its final state, the meander-like super-structure is crystalline, as revealed by time-resolved wide-angl…
Bulk morphologies of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) triblock terpolymers
Abstract The self-assembly of block copolymers in the bulk phase enables the formation of complex nanostructures with sub 100 nm periodicities and long-range order, both relevant for nanotechnology applications. Here, we map the bulk phase behavior of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) (SBT) triblock terpolymers on a series of narrowly distributed polymers with widely different block volume fractions, ϕS, ϕB and ϕT. In dependence of ϕ, we find the lamella–lamella, core-shell cylinder, cylinder-in-lamella and core-shell gyroid morphology, but also a rarely observed cylinder-in-lamella phase. The bulk morphologies are thoroughly characterized by transmission e…
Synergistic effects of Janus particles and triblock terpolymers on toughness of immiscible polymer blends
Abstract By influencing both the interfacial adhesion and the morphology, compatibilizers determine the mechanical properties of polymer blends. Here, we study the mechanical properties, in particular the fatigue crack propagation (FCP) of immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether)/poly(styrene- co -acrylonitrile) (PPE/SAN), compatibilized with Janus nanoparticles (JPs) and linear polystyrene- block -polybutadiene- block -poly(methyl methacrylate) (SBM) triblock terpolymers. Synergistic effects of a mixture of both compatibilizers improve the FCP behavior and reveal the important role of interface stiffness and flexibility on the mechanical properties of polymer blends. The…
The Impact of Janus Nanoparticles on the Compatibilization of Immiscible Polymer Blends under Technologically Relevant Conditions
Several hundred grams of Janus nanoparticles (d ≈ 40 nm) were synthesized from triblock terpolymers as compatibilizers for blending of technologically relevant polymers, PPE and SAN, on industry-scale extruders. The Janus nanoparticles (JPs) demonstrate superior compatibilization capabilities compared to the corresponding triblock terpolymer, attributed to the combined intrinsic properties, amphiphilicity and the Pickering effect. Straightforward mixing and extrusion protocols yield multiscale blend morphologies with "raspberry-like" structures of JPs-covered PPE phases in a SAN matrix. The JPs densely pack at the blend interface providing the necessary steric repulsion to suppress droplet …