Towards a consistent mechanism of emulsion polymerization—new experimental details

The application of atypical experimental methods such as conductivity measurements, optical microscopy, and nonstirred polymerizations to investigations of the ‘classical’ batch ab initio emulsion polymerization of styrene revealed astonishing facts. The most important result is the discovery of spontaneous emulsification leading to monomer droplets even in the quiescent styrene in water system. These monomer droplets with a size between a few and some hundreds of nanometers, which are formed by spontaneous emulsification as soon as styrene and water are brought into contact, have a strong influence on the particle nucleation, the particle morphology, and the swelling of the particles. Experimental results confirm that micelles of low-molecular-weight surfactants are not a major locus of particle nucleation. Brownian dynamics simulations show that the capture of matter by the particles strongly depends on the polymer volume fraction and the size of the captured species (primary free radicals, oligomers, single monomer molecules, or clusters)

Polyamide capsules via soft templating with oil drops—1. Morphological studies of the capsule wall

Poly(terephthalamide) microcapsules can be reproducibly and easily prepared by interfacial polycondensation around emulsion droplets in water. Oil drops of cyclohexane/chloroform mixture stabilized with poly(vinyl alcohol) containing terephthaloylchloride serve as soft template. The interfacial polycondensation starts immediately after addition of an amine mixture (hexamethylenediamine/diethylenetriamine). Light and scanning electron microscopy prove the formation of capsules with size distribution in the range from a few up to 100 µm depending on particular composition of the reaction mixture. The morphology of the capsule wall is characterized by precipitated particles. If instead of pure organic solvents a reactive oil phase is used as template, the capsules can serve in subsequent reactions as templates for the synthesis of composite particles. In this way, styrene can be radically polymerized inside the capsule leading to composite capsules. The capsule morphology is determined by the partition of all components between all phases