Film Formation and Polymer Diffusion in Poly(vinyl acetate-co-butyl acrylate) Latex Films. Temperature Dependence

We describe polymer diffusion measurements in a poly(vinyl acetate) copolymer latex film by fluorescence decay measurements of nonradiative energy transfer (FRET). The base monomer is a 4:1 weight ratio copolymer of vinyl acetate and butyl acrylate P(VAc−BA) with a glass transition temperature of ca. 12 °C. P(VAc−BA) latex particles labeled with phenanthrene (Phe) as the donor and with 4-( N, N -dimethylamino)benzophenone (NBen) as the acceptor were prepared by semicontinuous emulsion polymerization. Latex films were cast from a 1:1 mixture of Phe- and NBen-labeled latex samples. First, a series of films containing NBen-labeled latex samples with different NBen levels were annealed at 45 °C, showing that NBen levels have no influence on the rate of polymer diffusion in P(VAc−BA) latex films. From the fully mixed solvent-cast films, the characteristic distance for energy transfer between Phe and NBen (the Förster radius R 0 ) was obtained as 2.44 nm. Then, polymer diffusion was monitored as a function of annealing temperature in latex films containing Phe-labeled latex with 1 mol % PheMA and NBen-labeled latex with 0.3 mol % of the NBen chromophore. The temperature dependence of the diffusion rate (from 35 to 75 °C) was characterized by an effective activation energy E a = 34 ± 0.5 kcal/mol. In parallel, an effective E a = 34 kcal/mol was obtained from viscoelastic relaxation measurements over a range of temperatures close to those of the diffusion experiments.