Self-assembling properties of poly(sodium acrylate) grafted with dodecyl [C12], PAAgC12,
or poly(N-isopropylacrylamide) [PNIPA] side chains, PAAgPNIPA, were studied in unentangled semidilute
aqueous solution. While PAAgC12 self-associates through hydrophobic interactions, the gelation of
PAAgPNIPA is triggered by heating in response to the lower critical solution temperature of PNIPA
(LCST ∼ 32 °C). The local structure of the physical networks was investigated by small-angle neutron
scattering, and the scattering patterns were described using a polydisperse sphere model taking into
account hard-sphere interactions. This model allow us to draw a realistic picture of physical gels with
quantitative information concerning the size of hydrophobic cores, the volume fraction of stickers in the
aggregates, the fraction of stickers which take part in the aggregation process, the range of repulsive
interactions, and the structural modifications induced by temperature. The description of the network is
in good agreement with complementary data obtained from DSC and 13C NMR. In the present work, a
special emphasis has been given to the important relationship existing between the viscoelastic properties
of associating polymer solutions and the binding energy of stickers leaving temporarily the micellar
junction. Depending on the endothermic or exothermic nature of the disengagement process of the sticker
(heat of demicellization), the relaxation time of the network and the viscoelastic properties will either
decrease or increase with the temperature. The consequence is that aqueous solutions of PAAgC12 and
PAAgPNIPA exhibit opposite rheological properties with the temperature, namely thermothinning and
thermothickening. By mixing these two copolymers, we show that intermediate properties can be obtained
but in that case a microphase-separated network is obtained as a result of copolymer segregation.
Articles you may be interested inShear-induced structure in polymer blends with viscoelastic asymmetry Abstract. Self-assembling and viscoelastic properties of thermothinning and thermothickening copolymers are described in semi-dilute aqueous solutions. Using grafted architectures derived from poly(sodium acrylate), we also investigate the possibilities to combine alkyl and LCST stickers, either grafted on different polymer chains or incorporated into the same macromolecule (double grafted copolymers), to control the temperature dependence of aqueous based formulations.
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