Core-shell reversible particle precipitation from aqueous di-stimuli-responsive diblocks is demonstrated as also is the interconversion from one core-shell combination to the other.

Summary: The paper provides experimental results about an easy and versatile method to produce amphiphilic block copolymers, block copolymer particles, and even inorganic – polymeric nano‐composites via aqueous heterophase polymerization. Special emphasis is placed on the morphology and colloidal properties of some non‐ionic di‐ and triblock copolymer particles with poly(ethylene glycol) of 106 g/mol molecular weight as hydrophilic block as well as di‐stimuli‐responsive block copolymers containing both a poly(N‐isopropyl acrylamide) and a poly(ionic liquid) block.

A comprehensive experimental study of thermally initiated styrene‐styrene sulfonate emulsion copolymerization in the presence of 15 different low‐molecular‐weight electrolytes clarifies the enormous influence of both the concentration and nature of the added salt on the outcome of the polymerization. The ionic strength (IS) has a direct influence on the styrene sulfonate content in the final copolymer and determines whether the physical state of the final reaction product is a solution or dispersion. Stable latexes have been obtained for IS as high as 18 M. Electron microscopy images show irregularly shaped clusters at low and spherical particles at high IS. The properties of the copolymer molecules and dispersion can be additionally modified by the chemical properties of the counter‐ and coions introduced with the salt.magnified image

Summary: The paper considers various possibilities to produce inorganic -polymeric nanocomposites via aqueous heterophase polymerization. Special emphasis is placed on strategies to synthesize nanocomposite particles via joint nucleation or joint polymerization. The former strategy is used to make composite particles with CaCO 3 as inorganic component. The strategy of joint polymerization takes advantage from the condition that aqueous heterophase polymerization is a convenient possibility to synthesize amphiphilic block copolymers. This method relies on the fact that polymeric radicals can survive in isolated latex particles that are stabilized by hydrophilic blocks. This strategy can be successfully applied to produce silicacontaining block copolymer particles in a one-step procedure.

Cryo-electron microscopy, atomic force microscopy, and light microscopy investigations provide experimental evidence that amphiphilic emulsion copolymerization particles change their morphology in dependence on concentration. The shape of the particles is spherical at solids content above 1%, but it changes to rod-like, ring-like, and web-like structures at lower concentrations. In addition, the shape and morphology of these particles at low concentrations are not fixed but very flexible and vary with time between spheres, flexible pearl-necklace structures, and stretched rods.

Summary: Experimental data are discussed challenging the deterministic kinetics of emulsion polymerization. Examples are given for the overall rate of polymerization, in‐situ stabilizer formation, and swelling of latex particles. Improving the deterministic view on emulsion polymerization kinetics requires the consideration of results of molecular modelling and the application of multiscale integration techniques.

Multiple suspension particles — a new morphology of polymer particles — are generated on the verge of colloidal stability in the course of redox-initiated aqueous heterophase copolymerization. These particles consist of block copolymers which are arranged in the form of a micrometer-sized poly(N-isopropylacrylamide) physical network as scaffold containing nanometer-sized particles of hydrophobic polymers covalently attached