ABSTRACT
A homologous series of thermoassociating copolymers was prepared by grafting onto alginates different amounts of three different temperature responsive polymers: poly(N-isopropylacrylamide), poly(di(ethylene glycol)methacrylate) and poly(ethylene oxide-co-propylene oxide). From a large set of analytical techniques combining rheology, calorimetry, NMR and SAXS, the relevant parameters controlling the sol/gel transition and the gel properties, mainly the degree of entanglement of macromolecules and the fraction of responsive stickers, were highlighted and interpreted objectively by considering the particularities of the phase diagrams of LCST polymers. Complementary analyses were implemented to investigate adhesiveness, injectabilty, gel swelling and molecular release in physiological environment of thermogelling formulations. In particular, it is shown that steady shear experiments allow to predict the injection forces by taking into account the characteristics of the system (syringe and needle), and that the rapid gelation of the formulations when they are heated at 37 °C delays the release of small molecules into the environment. The overall set of data is discussed in the framework of scaling relations in order to draw quantitative guidelines for the design of injectable thermoresponsive hydrogels.
ABSTRACT
HYPOTHESIS: Dispersions of Laponite in water may form gels, the rheological properties of which being possibly tuned by the addition of polymer chains. Laponite-based hydrogels with poly(ethylene oxide) (PEO) were the most widely investigated systems and the PEO chains were then found to reduce the elastic modulus. EXPERIMENTS: Here, hydrogels based on Laponite and poly(2-methyl-2-oxazoline) (POXA) were considered. The adsorption behavior and the local structures within these nanocomposite gels were investigated by small-angle neutron scattering and NMR. The same materials were macroscopically characterized using rheology. FINDINGS: An original evolution of the storage modulus G' with the POXA concentration is evidenced compared to Laponite/PEO hydrogels. At low POXA concentrations, a continuous reduction of G' is observed upon increasing the polymer content, as with PEO, due to the screening of electrostatic interactions between the clay platelets. However, above a critical value of the POXA concentration, G' increases with the polymer content. This difference with PEO-based hydrogels is correlated to the stronger affinity of POXA chains for the clay surfaces, which results in the reduction of the inhomogeneities for the Laponite disks within the gels. Steric repulsions would then counterbalance the effect of electrostatic repulsions and lead to the strengthening of the POXA-based hydrogels.
ABSTRACT
The PDMS lamellar sublayers of a poly(styrene)-poly(dimethylsiloxane) diblock (PS-PDMS) and PS-PDMS-PS triblocks are investigated by NMR and dielectric spectroscopy. Some segments of the confined PDMS chains display anisotropic orientational fluctuations along the interfaces with the PS glassy blocks, whereas the others display fluctuations rather parallel to the lamellae normal. This coexistence results from a competitive ordering effect induced by the glassy interfaces and the chain-end anchoring junctions. The distribution of PDMS relaxation times within the sublayers is also examined: in particular, a slowing down of the segmental motions, together with a broadening of this distribution, are detected.
ABSTRACT
The segmental dynamics of PVME within the single-phase state of poly(styrene)/poly(vinyl methyl ether) blends (PS/PVME) was examined by dielectric spectroscopy. A particular attention has been given to the high PS concentration regime. In this latter, rather localized, weakly cooperative motions of the PVME segments are detected at low temperatures, in addition of the secondary relaxation processes. This feature is attributed to confinement effects induced by the PS chains on the PVME.
ABSTRACT
The segmental ordering within a lamellar polystyrene-polydimethylsiloxane diblock (PS-PDMS) was examined by NMR. A non-uniform stretching of the PDMS chains was evidenced. Although chain segments displaying isotropic reorientational motions are present along the chains, relaxation measurements on the free PDMS extremities demonstrate that these latter are oriented and submitted to a non-zero constraint. This specific result allows to precise some features of the order distribution within the lamellae.
