Structure of Self-Initiated Photopolymerized Films: A Comparison of Models

Self-initiated photografting and photopolymerization (SI-PGP) uses UV illumination to graft polymers to surfaces without additional photoinitiators using the monomers as initiators, "inimers". A wider use of this method is obstructed by a lack of understanding of the resulting, presumably heterogeneous, polymer structure and of the parallel degradation under continuous UV illumination. We have used neutron reflectometry to investigate the structure of hydrated SI-PGP-prepared poly(HEMA-co-PEG₁₀MA) (poly(2-hydroxyethyl methacrylate-co-(ethylene glycol)₁₀ methacrylate)) films and compared parabolic, sigmoidal, and Gaussian models for the polymer volume fraction distributions. Results from fitting these models to the data suggest that either model can be used to approximate the volume fraction profile to similar accuracy. In addition, a second layer of deuterated poly(methacrylic acid) (poly(dMAA)) was grafted over the existing poly(HEMA-co-PEG₁₀MA) layer, and the resulting double-grafted films were also studied by neutron reflectometry to shed light on the UV-polymerization process and the inevitable UV-induced degradation which competes with the grafting.