Cross-Linking, Miscibility, and Interface Structure in Blends of Poly(2-ethylhexyl methacrylate) Copolymers. An Energy Transfer Study

We describe the miscibility of blends involving poly(ethylhexyl methacrylate) [PEHMA] latex copolymers using the direct nonradiative energy transfer (DET) technique. When the polymers in both components of a blend are PEHMA homopolymers, we obtain a fully mixed film. When one of the components in the blend is replaced with a PEHMA copolymer containing 5 mol % tert-butylcarbodiimidoethyl methacrylate (tBCEMA), we also obtain a fully mixed film. However, if a PEHMA copolymer containing 11 mol % methacrylic acid (MAA) is mixed with PEHMA homopolymer, the miscibility between the polymers is limited and is reduced further when the amount of MAA is increased to 20 mol %. Using a distribution model for energy transfer, we were able to determine the evolution of the interface thickness with annealing time. The maximum interface thickness attained in these blends decreases from δ = 15 nm to δ = 8 nm when the content of MAA in the blends increases from 11 mol % to 20 mol %. A freshly formed solvent-cast film prepared from a 1:1 blend of the PEHMA copolymer containing 11 mol % MAA and the PEHMA copolymer containing 5 mol % tBCEMA exhibits some polymer segregation. This persists in the solid film when the film is annealed for short times (20 min) at 60 °C. Over longer times, mixing of the copolymers occurs and reaches completion. We attribute this increase in miscibility to the formation of graft copolymer, which serves as a compatibilizing agent, through the reaction between the −COOH and −NCC− groups. When a film of the same composition is prepared from a blend of the two latex dispersions and annealed, a fully mixed film also results.