A. Gutowska et al., THERMOSENSITIVE INTERPENETRATING POLYMER NETWORKS - SYNTHESIS, CHARACTERIZATION, AND MACROMOLECULAR RELEASE, Macromolecules, 27(15), 1994, pp. 4167-4175
Thermosensitive semiinterpenetrating polymer networks (semi-IPNs) comp
osed of cross-linked poly(N-isopropylacrylamide) (NiPAAm) and linear p
oly(ether(urethane-urea) (Biomer) were obtained via UV-initiated solut
ion polymerization. The semi-IPNs exhibited negative thermosensitivity
, i.e., lower swelling levels with increasing temperature. The incorpo
ration of a relatively small content of Biomer (up to 10 wt %) strongl
y influenced the mechanical properties, equilibrium swelling, and desw
elling kinetics of synthesized networks. The semi-IPNs exhibited great
er mechanical strength compared to the cross-linked poly(NiPAAm). Equi
librium swelling levels of the semi-IPNs at low temperatures were mark
edly decreased due to hydrophobic contribution of Biomer and higher ap
parent effective cross-linking densities of these networks. The gel co
llapse point, related to the lower critical solution temperature of po
ly(NiPAAm), was not affected. The semi-IPNs showed much faster deswell
ing rates compared to the cross-linked poly(NiPAAm). It was hypothesiz
ed that the presence of Biomer prevented the formation of a skin-type
layer which normally retards the deswelling process of cross-linked po
ly(NiPAAm). Loading and release of heparin, a model macromolecule, was
studied as a function of temperature and Biomer content in semi-IPNs.
The partition coefficients of heparin within the networks decreased w
ith increasing temperature and Biomer content. Similarly, a linear rel
ationship between partition coefficients and equilibrium swelling in l
oading solutions was found for all synthesized networks. Heparin relea
se profiles correlated with deswelling kinetics of cross-linked poly(N
iPAAm) and NiPAAm/Biomer semi-IPNs. Release profiles were in agreement
with the proposed mechanism of solute release from swollen thermosens
itive gels.