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)

Conditions for secondary particle formation in emulsion polymerization systems

A simple means is deduced for determining conditions for secondary particle formation in emulsion polymerization systems in systems where the amount of added surfactant is below the cmc. A new radical formed from initiator in the aqueous phase will undergo some polymerization with aqueous-phase monomer, but must have three possible eventual fates: aqueous-phase termination, entry into a pre-existing particle, or creation of a new particle. The means for determining the onset and extent of secondary nucleation is to modify HUFT theory to take into account a successful model for entry [Macromolecules, 24, 1629 (1991)] which states that entry occurs if and only if the aqueous-phase radical has achieved a critical degree of polymerization z. Particle formation below the cmc is by homogeneous/coagulative nucleation which (if coagulation is ignored) gives an upper bound to the rate of formation of precursor particles; these are of a degree of polymerization j(crit) > z. The resulting equations are readily solved, and require only a knowledge of the aqueous-phase propagation and termination rate coefficients (the latter is very high: ca. 10(9) dm(3) mol(-1) s(-1) for termination between the very small radicals), z and j(crit). Easily applied means are given for estimating all these quantities. The treatment gives good accord with experimentally observed conditions for the onset of secondary nucleation in low-surfactant systems (including taking in situ micellization into account)