• Macromolecular Research
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• 제15권2호
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• pp.160-166
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• 2007

Novel multiblock copolymers, based on segmented sulfonated hydrophilic-hydrophobic blocks, were synthesized and investigated for their application as proton exchange membranes. A series of segmented sulfonated poly(arylene ether sulfone)-b-polyimide multiblock copolymers, with various block lengths, were synthesized via the coupling reaction between the terminal amine moieties on the hydrophilic blocks and naphthalene anhydride functionalized hydrophobic blocks. Successful imidization reactions required a mixed solvent system, comprised of NMP and m-cresol, in the presence of catalysts. Proton conductivity measurements revealed that the proton conductivity improved with increasing hydrophilic and hydrophobic block lengths. The morphological structure of the multiblock copolymers was investigated using tapping mode atomic force microscopy (TM-AFM). The AFM images of the copolymers demonstrated well-defined nanophase separated morphologies, with the changes in the block length having a pronounced effect on the phase separated morphologies of the system. The self diffusion coefficient of water, as measured by $^1H$ NMR, provided a better understanding of the transport process. Thus, the block copolymers showed higher values than Nafion, and comparable proton conductivities in liquid water, as well as under partially hydrated conditions at $80^{\circ}C$. The new materials are strong candidates for use in PEM systems.

• Bulletin of the Korean Chemical Society
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• 제22권5호
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• pp.467-475
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• 2001

A triblock copolymer based on $poly(\varepsilon-caprolactone)$ (PCL) as the hydrophobic part and poly(ethylene glycol) (PEG) as the hydrophilic portion was synthesized by a ring-opening mechanism of ${\varepsilon}-caprolactone$ with PEG containing a hydroxyl group at bot h ends as an initiator. The synthesized block copolymers of PCL/PEG/PCL (CEC) were confirmed and characterized using various analysis equipment such as 1H NMR, DSC, FT-IR, and WAXD. Core-shell type nanoparticles of CEC triblock copolymers were prepared using a dialysis technique to estimate their potential as a colloidal drug carrier using a hydrophobic drug. From the results of particle size analysis and transmission electron microscopy, the particle size of CEC core-shell type nanoparticles was determined to be about 20-60 nm with a spherical shape. Since CEC block copolymer nanoparticles have a core-shell type micellar structure and small particle size similar to polymeric micelles, CEC block copolymer can self-associate at certain concentrations and the critical association concentration (CAC) was able to be determined by fluorescence probe techniques. The CAC values of the CEC block copolymers were dependent on the PCL block length. In addition, drug loading contents were dependent on the PCL block length: the larger the PCL block length, the higher the drug loading content. Drug release from CEC core-shell type nanoparticles showed an initial burst release for the first 12 hrs followed by pseudo-zero order release kinetics for 2 or 3 days. CEC-2 block copolymer core-shell type nanoparticles were degraded very slowly, suggesting that the drug release kinetics were governed by a diffusion mechanism rather than a degradation mechanism irrelevant to the CEC block copolymer composition.