The reactive formation of diblock copolymer at a polymer/polymer interface and its effect on interfacial structure

The reaction of perdeuterated amino-terminal polystyrene (dPS-NH₂) with anhydride-terminal poly(methyl methacrylate) (PMMA-anh) at a PS/PMMA interface has been observed with forward recoil spectrometry (FRES). Bilayer samples were constructed by placing thin films of PS containing ∼8.5 wt% dPS-NH₂ on a PMMA-anh layer. Significant reaction was observed only after annealing the samples at 174°C for several hours, a time scale at least two orders of magnitude greater than the time required for the dPS-NH₂ chains to diffuse through the bulk PS layer. The topography of the interfacial region as copolymer formed was measured using atomic force microscopy (AFM). Roughening of the PS/PMMA interface was observed to varying degrees in all annealed samples. Furthermore, the extent of this roughening was found to depend on the PS matrix molecular weight. Reaction in the samples with a high molecular weight PS matrix resulted in a root mean square roughness approximately equal to the radius of gyration R_g of the copolymer. However, approximately twice as much roughening was observed in the low molecular weight PS matrix. This study reveals how the molecular weight of one of the phases can affect the rate of reaction at a polymer/polymer interface.