Abstract
<jats:p> Surface-compartmentalized micelles (patchy or Janus-type) show an outstanding interfacial activity, making them highly attractive for various applications. In this project alternative routes to surface-compartmentalized micelles were developed based on crystallization- (CDSA) and stereocomplex-driven self-assembly (SCDSA) of polylactide (PLA)-based block copolymers. SCDSA of diblock copolymers bearing enantiomeric poly( <jats:italic toggle="yes">L</jats:italic> -lactide)/poly( <jats:italic toggle="yes">D</jats:italic> -lactide) blocks and highly incompatible corona-forming blocks (polystyrene (PS) and poly( <jats:italic toggle="yes">tert</jats:italic> -butyl methacrylate) (P <jats:italic toggle="yes">t</jats:italic> BMA)) was introduced as facile method to prepare uniform spherical micelles with a semicrystalline stereocomplex (SC) core, formed by the enantiomeric PLA blocks, and a shamrock-like microphase-separated PS/P <jats:italic toggle="yes">t</jats:italic> BMA corona. The patchy micelles showed a significantly higher interfacial activity compared to micelles with a homogenous PS corona and were also successfully employed in the stabilization of emulsions and as compatibilizers in strongly incompatible PS/P <jats:italic toggle="yes">t</jats:italic> BMA blends. The excellent performance of patchy micelles is attributed to their adaptive corona that enables selective swelling/collapse of the respective miscible/immiscible patches at the emulsion or blend interface. However, with SCDSA other morphologies (cylinders, platelets) could not be realized. </jats:p> <jats:p> Co-crystallization-driven self-assembly (CCDSA) of PS- <jats:italic toggle="yes">b</jats:italic> -P <jats:italic toggle="yes">L</jats:italic> LA- <jats:italic toggle="yes">b</jats:italic> -P <jats:italic toggle="yes">t</jats:italic> BMA (SLT) triblock terpolymers with the corresponding P <jats:italic toggle="yes">L</jats:italic> LA homopolymer gave for the first time access to platelet-like micelles, featuring a non-concentric, nanometre-sized, stripe-patterned corona. Depending on the length of the employed P <jats:italic toggle="yes">L</jats:italic> LA homopolymer either twisted patchy platelet or defined pyramidal structures composed of stacked patchy platelets can be produced. Interestingly, the neat SLT assembled to Janus micelles with an amorphous P <jats:italic toggle="yes">L</jats:italic> LA core, attributed to the strongly hindered crystallization of the P <jats:italic toggle="yes">L</jats:italic> LA middle block. The interfacial activity of the patchy platelets is significantly higher compared to spherical patchy micelles, and they proved effective in stabilizing emulsions. </jats:p> <jats:p> Finally, CDSA and SCDSA were combined to selectively load the P <jats:italic toggle="yes">L</jats:italic> LA patches within patchy worm-like micelles formed by a double-crystalline PS- <jats:italic toggle="yes">b</jats:italic> -PE- <jats:italic toggle="yes">b</jats:italic> -P <jats:italic toggle="yes">L</jats:italic> LA (PE = polyethylene) triblock terpolymer. When CDSA is conducted in THF only the PE middle block crystallized and worm-like micelles with a crystalline PE core and an amorphous, patchy PS/P <jats:italic toggle="yes">L</jats:italic> LA corona were formed. Subsequently, the P <jats:italic toggle="yes">L</jats:italic> LA patches were selectively loaded via stereocomplexation with an enantiomeric P <jats:italic toggle="yes">D</jats:italic> LA homopolymer, yielding micelles with P <jats:italic toggle="yes">L</jats:italic> LA/P <jats:italic toggle="yes">D</jats:italic> LA SC domains in the corona showing a significantly increased size. </jats:p> <jats:p>This project revealed the excellent potential of stereoregular PLA-based block copolymers for the preparation of surface-compartmentalized micelles of varying shape and tailored corona functionalities utilizing SCDSA and CCDSA.</jats:p>