We report a blending mechanism of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) and PS homopolymer (homoPS) at the air/water interface. Our blending mechanism is completely different from the well-known “wet–dry brush theory” for bulk blends; regardless of the size of homoPS, the domain size increased and the morphology changed without macrophase separation, whereas the homoPS of small molecular weight (MW) leads to a transition after blending into the block copolymer domains, and the large MW homoPS is phase-separated in bulk. The difference in blending mechanism at the interface is attributed to adsorption kinetics at a water/spreading solvent interface. Upon spreading, PS-b-PEO is rapidly adsorbed to the water/spreading solvent interface and forms domain first, and then homoPS accumulates on them as the solvent completely evaporates. On the basis of our proposed mechanism, we demonstrate that rapid PS-b-PEO adsorption is crucial to determine the final morphology of the blends. We additionally found that spreading preformed self-assemblies of the blends slowed down the adsorption, causing them to behave similar to bulk blends, following the “wet–dry brush theory”. This new mechanism provides useful information for various block copolymer-homopolymer blending systems with large fluid/fluid interfaces such as emulsions and foams.

We report on the phase separation behaviors of polymerization mixtures containing a polylactide macro-chain transfer agent (PLA-CTA), styrene, divinylbenzene, hydroxyl-terminated PLA (PLA-OH), and a molecular chain transfer agent which enable the ability to tune the pore size of a cross-linked polymer monolith in a facile manner. Cross-linked monoliths were produced from the mixtures via reversible addition-fragmentation chain transfer (RAFT) polymerization and converted into cross-linked porous polymers by selective removal of PLA while retaining the parent morphology. We demonstrate that pore sizes are tunable over a wide range of length scales from the meso- to macroporous regimes by adjusting the ratio of PLA-CTA to PLA-OH in the reaction mixture which causes the phase separation mechanism to change from polymerization-induced microphase separation to polymerization-induced phase separation. The possibility of increasing porosity and inducing simultaneous micro- and macrophase separation was also realized by adjustments in the molar mass of PLA which enabled the synthesis of hierarchically meso- and macroporous polymers.