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        Synthesis and Sol-Gel Transition of Novel Temperature Responsive ABA Triblock-Graft Copolymers Based on PCL and PEG Analogues

        Qinqin Wang,Shouxin Liu,Weijuan Sheng,Naer Guang,Xuan Li 한국고분자학회 2015 Macromolecular Research Vol.23 No.7

        Novel hydrophilic, temperature responsive, and biodegradable ABA triblock-graft copolymers, [poly(ε- caprolactone)-g-poly(2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate)]-b-poly(ethylene glycol)-b-[poly(-caprolactone)-g-poly(2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate)] ([PCL-g-P(MEO2MA-co-OEGMA)]-b-PEG-b-[PCL-g-P(MEO2MA-co-OEGMA)]) (tBGs), were synthesized via a combination of ring-opening polymerization (ROP) of ε-caprolactone (εCL) and α-chloro-ε-caprolactone (αClεCL) in the presence of PEG and atom transfer radical polymerization (ATRP) of MEO2MA and OEGMA. Temperature responsive P(MEO2MA-co-OEGMA) graft chains on the hydrophobic PCL block of PCL-b-PEG-b-PCL not only improved the solubility of PCL-b-PEG-b-PCL in water, but also endowed it with temperature sensitivity. The synthesized temperature responsive triblock-graft copolymers formed well-defined core-shell micelles as the temperature was above their LCST (ca. 35 oC), with hydrophilic PEG block as shell, P(MEO2MA-co-OEGMA) graft chains on the PCL block and hydrophobic PCL block aggregates as core. The micellization induced by temperature for the tBGs in aqueous solutions had been investigated by transmittance measurement, laser particle size measurement, 1H NMR in D2O, DLS and TEM. For a given tBG5 aqueous solution (30 wt%), a weak hydrogel was available at 35 oC, and its sol-gel transition temperature gradually decreased with increasing concentration. In addition, the tBG5 hydrogels loaded with anethole were used for hydrophobic drug release, and in vitro the sustained release of anethole from the tBG5 hydrogels was examined, which is a significant for anethole for their biomedical applications.

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