INVESTIGADORES
CAREGNATO Paula
artículos
Título:
Kinetics studies of the sulfate radical-initiated polymerization of vinyl acetate and 4-vinylpyridine in the presence of silica nanoparticles.
Autor/es:
PAULA CAREGNATO; GALO CARRILLO LE ROUX; DANIEL O. MÁRTIRE; MÓNICA C. GONZALEZ
Revista:
LANGMUIR
Editorial:
American Chemical Society
Referencias:
Lugar: Washington D.C. , US.; Año: 2005 vol. 21 p. 8001 - 8009
ISSN:
0743-7463
Resumen:
The photolysis of silica suspensions of pH ~ 8 containing peroxodisulfate ions leads to the generation
of two surface transients with a distinct spectrum and reactivity. Time-resolved and continuous irradiation
experiments of similar dispersions also containing variable concentrations of vinyl acetate (VA) or 4-vinyl
pyridine (4-VP) allowed the evaluation of the contribution of silica/water interfacial reactions to the kinetics
and structural pattern of polymers synthesized using sulfate radicals as initiators. The rate constants
measured for the reactions of the surface transients with 4-VP are 1 order of magnitude higher than those
of VA, despite the fact that both species show similar reactivity in homogeneous solution toward sulfate
radicals. It is suggested that both the sorption capacity and the different specific interactions with the
silica surface of 4-VP and VA contribute to the observed reaction rates. Micrometer-sized latex particles
of 4-VP and VP showed higher stability and more homogeneous size distributions when obtained in the
presence of silica nanoparticles. Under the experimental conditions required for obtaining polymer particles,
both the contribution of the described interfacial reactions and the effect of silica adsorbed monomer on
the initiation steps of the polymerization may be neglected. The importance of in situ adsorption of the
oligomer/polymer chains to silica NP during the polymerization propagation steps in determining the
particle morphology is discussed.
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