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Novel mixed micelle was successfully fabricated by the synergistic self-assembly of poly(methacrylate isobutyl polyhedral oligomeric silsesquioxane (POSS)-co-N-isopropylacrylamide-co-oligo(ethylene glycol)methyl ether methacrylate-co-acrylic acid) (P(methacrylate isobutyl (MAPOSS)-co-NIPAM-co-OEGMA-co-AA)) and poly(methacrylate isobutyl POSS-co-N-isopropylacrylamide-co-oligo(ethylene glycol) methyl ether methacrylate-co-2-vinylpyridine) (P(MAPOSS-co-NIPAM-co-OEGMA-co-2VP)). Dynamic light scattering (DLS) and transmission electron microscopy characterizations demonstrate that the formation of mixed micelles is driven by electrostatic interaction. The formation of the mixed micelles was further implied by a simple fluorescence resonance energy transfer based technique. The mixed micelle possesses the biggest size at pH = 7.0, which is attributed to the strongest electrostatic interaction between the two kinds of micelles. The zeta potential under different pH was detected to further investigate the surface charges corroborating the discussions. DLS and UV-vis indicate that the lower critical solution temperature (LCST) is pH dependent. The mixed micelles reach the highest LCST at pH 7.0. The LCST of the mixed micelle can be tuned by adjusting the volume ratio of the two kinds of micelles as well. Moreover, the thermo-responsive behavior of the mixed micelle is absolutely reversible.
In this study, a novel hybrid block copolymer containing POSS (BCP), poly(methacrylisobutyl-POSS)-b-poly(methylmethacrylate) (PMAiBuPOSS-b-PMMA) was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The structure and molecular weight were characterized via 1H NMR and GPC. BCP was creatively used as the compatibilizer to overcome the bad compatibility of epoxy and POSS in their blend system. SEM and dynamic mechanical thermal analyses (DMTA) were used to observe the surface morphology and thermal–mechanical behaviors of the resultant products. We found that the amount of microaggregation domains of POSS decreased, while the nano ones increased, when BCP content increased. All the aggregation domains were distributed in epoxy matrix uniformly at nanoscale with the addition of 10 phr BCP and 5 phr POSS monomers. The results indicated that BCP could effectively improve the compatibility between epoxy resin and POSS owing to its amphiphilicity in DGEBA. The fracture behavior of products transformed from brittle fracture to ductile fracture gradually with the increase of BCP, whereas the Tg and E′ decreased.
Novel hybrid diblock copolymers consisting of bidentate ligand-functionalized chains have been synthesized via click reaction and RAFT radical polymerization. The chemical structure and molecular weight of the synthesized poly(methacrylate-POSS)-block-poly(4-vinylbenzyl-2-pyridine-1H-1,2,3-triazole) (PMAPOSS-b-PVBPT) were characterized by NMR and GPC. The copolymers had been utilized to construct metal-containing polymer micelle by the metal–ligand coordination and electrostatic interaction in this study. The self-assembly behaviors of PMAPOSS-b-PVBPT in chloroform, a common solvent, under the effect of Zn(OTf)2 and HAuCl4 were investigated by TEM, DLS, and variable temperature NMR. Besides, micellization of this diblock copolymer was achieved in ethylene glycol, a selective solvent for PMAPOSS-b-PVBPT. The experimental results revealed that the incorporation of heterocyclic rings bearing nitrogen atoms in polymer side chains played an important role in the construction of metal-containing copolymer micelles. The prepared metal-containing PMAPOSS-b-PVBPT micelles had good dynamic and thermal stability due to the strong metal–ligand coordination interaction and electrostatic interaction.
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