Grafting Bimodal Polymer Brushes on Nanoparticles Using Controlled Radical Polymerization

Abstract

RAFT (reversible addition–fragmentation chain transfer) polymerization has been widely used to synthesize different polymer architectures such as polymer brushes on nanoparticles for incorporation into polymer nanocomposites. It is believed that these polymer brushes, with the same chemistry as the matrix polymer, can be employed to improve filler dispersion by compatibilizing unfavorable enthalpic interactions between the inorganic nanoparticles and their organic host matrices. However, monomodal brush graft nanoparticles are found to aggregate into a range of isotropic and anisotropic morphologies, formed due to a delicate balance between enthalpic and entropic interfacial interactions. This coupling of enthalpy and entropy leaves only a small window of graft densities and molecular weights to obtain randomly dispersed filler morphologies. These issues can be countered by using a bimodal polymer brush that contains a small number of long homopolymer chains that can entangle, and a high density of short brushes that screens the particle/particle attraction, thereby aiding in decoupling the interfacial enthalpic and entropic interactions. In the present work, we demonstrate a robust step-by-step technique using RAFT polymerization to synthesize these bidisperse/bimodal polymer brush-anchored nanoparticles. A layer of dense brush of the first population was initially prepared using surface-initiated RAFT polymerization from colloidal silica nanoparticles. After cleavage of the chain transfer agent from the first population of chain ends, a second RAFT agent was attached onto the silica nanoparticles and then a monomer, which may be the same or different from the first brush, was polymerized. This versatile and widely applicable route enables us to independently control the molecular variables of the attached chains, such as composition, molecular weights and graft densities of the individual populations. The bimodal brush-grafted colloidal silica nanoparticles show superior dispersion and interaction with a homopolymer matrix when compared to monomodal brush-grafted particles.