Blends of small particle size fluorinated acrylic copolymer latexes with a large particle size
styrene/acrylic copolymer latex were examined with regard to formation of low free energy surfaces,
amount of incorporated fluorinated copolymer, particle size, and particle size asymmetry. The styrene/acrylic latex was prepared by emulsion polymerization of n-butyl acrylate and styrene. Several varieties
of fluorinated latexes were prepared. One was prepared by copolymerization of n-butyl acrylate and the
fluorinated monomer, FMA, H2CC(CH3)CO2(CH2)2(CF2)
n
F (n̄ ≈ 7.7). Two types of copolymer core/fluorinated copolymer shell latex systems were prepared. One was comprised of a highly cross-linked
core of poly(divinylbenzene) and a shell of poly(n-butyl acrylate-co-FMA). The other had a lightly cross-linked core of poly(n-butyl acrylate-co-divinylbenzene) and a shell of poly(n-butyl acrylate-co-FMA). Films
cast from blends of styrene/acrylic and fluorinated copolymer latexes were examined by contact angle
goniometry, X-ray photoelectron spectroscopy (XPS), time-of-flight static secondary ion mass spectroscopy
(ToF-SIMS), and tapping mode atomic force microscopy (TMAFM). In some cases, low free energy surfaces
were created at small mole fractions (∼10-4−10-2) of fluorinated monomer copolymerized with acrylic
monomers in the mixture. AFM images were used to differentiate fluorinated, phase-segregated regions
in the mixtures. Because of the disparity in particle size (asymmetry) between the styrene/acrylic and
fluorine-containing latexes, the phenomena of percolation and excluded volume can be used to establish
a substantial excess of fluorinated, low free energy material at the surface of an asymmetric blend of the
two.
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