Modification of biocompatible elastomers, especially polydimethylsiloxane
(PDMS), through blending with hydrophilic excipients is sought in
various biomedical applications to enhance the affinity of the hydrophobic
polymer to water and increase the permeability of water vapor and
of bioactive substances. In this work, a rubbery poly(ethylene oxide)/poly(propylene
oxide)/poly(ethylene oxide) block copolymer, known as poloxamer 188
(POL), and glassy polyvinylpyrrolidone (PVP) were incorporated in
PDMS matrices at a 2.5–35% w/w content. POL, due to its amphiphilic
nature, was better dispersed in smaller spherical domains than PVP
in the matrix and exerted a stronger interfering effect on the curing
reaction of PDMS, as indicated by DSC data. The Young modulus of PDMS-POL
films decreased with increasing POL content and that of PDMS-PVP films
remained practically unaffected up to a 20% w/w PVP content and exhibited
an abrupt increase above 25% w/w. For a certain additive content,
the water uptake was higher in the PDMS-POL films and produced a controllable
and gradual increase in the permeability of caffeine over the whole
range of additive content studied. Above a 25% w/w content, the PDMS-PVP
films are characterized by a rather abrupt increase in caffeine permeability
values, well above the maximum increase predicted by Maxwell’s
model for strictly two-phase systems with fully discrete phase domains
of the dispersed phase. The effects of PVP and POL on the examined
properties of the modified PDMS matrices are discussed and interpreted
in relation to the morphological features of the films with increasing
additive content and the network characteristics of the PDMS phase.