AbstractThe ultimate objective of hybrid miniemulsion polymerization is to produce a water‐based crosslinkable coating through in situ grafting of a free radical growing acrylic polymer with an unsaturated resin. Certain authors have reported low grafting while others have reported higher. This article explores the factors that influence the grafting tendencies of these systems. Methacrylates such as methyl methacrylate (MMA) have a sterically hindered radical center that lowers its reactivity toward unsaturated resin. This steric hindrance from the methyl group forces grafting of this type of monomer to occur by abstraction of a hydrogen allylic to a resinous double bond. This chain transfer produces a relatively inactive radical on the resin that reduces the grafting efficiency. The transfer process also inherently produces some degree of terminated PMMA polymer within the particle. Grafting occurs in this type of system through termination of living PMMA chains with that radical produced on the resin. For relatively water‐soluble monomers such as MMA, grafting efficiency is further lessened by homogeneous nucleation resulting from the monomer hydrophilicity. These newly created particles cannot contain alkyd due to its hydrophobicity and thus inability to transport across the aqueous phase, and hence cannot produce grafted polymer. Nonetheless, degree of grafting of nearly 50% was observed in these systems. For hybrid systems involving an acrylate monomer such as butyl acrylate (BA), virtually complete grafting with alkyd was observed. This is due to the uninhibited BA radical center allowing the molecule to add directly through a resin double bond. This process offers the possibility for complete grafting. Homogeneous nucleation is not involved in this system due to the insolubility of BA in the aqueous phase. Resin double bond content and degree of conjugation also play an integral role in the grafting process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1825–1836, 2003
