• Macromolecular Research
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• v.10 no.6
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• pp.325-331
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• 2002

Phase behavior of a PEO-PPO-PEO (Pluronic P103) triblock copolymer in water is investigated using small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and rheology. Pluronic P103 shows apparent two gel states in different temperature regions. The first sol-to-gel transition at a lower temperature (i.e., the hard gel I state) turns out to be the hexagonal microphase as evidenced by the combined SANS and SAXS and the frequency dependence of both G′ and G" in rheology. In contrast to the hard gel I, the second sol-to-gel transition (i. e., the hard gel II state) at a higher temperature represents the block copolymer micelles in somewhat disordered state rather than the ordered state seen in the hard gel I. Moreover, turbidity change depending only on the temperature with four distinct regions is observed and the large aggregates with size larger than 5,000 nm are detected with DLS in the turbid solution region. Based upon the present study, two different gelation mechanisms for aqueous PEO-PPO-PEO triblock copolymer solutions are proposed.

• Macromolecular Research
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• v.17 no.5
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• pp.325-331
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• 2009

The synthesis and the characterization of crosslinked ABC triblock copolymer, i.e. polystyrene-b-poly (hydroxyethyl methacrylate)-b-poly(styrene sulfonic acid), (PS-b-PHEMA-b-PSSA) is reported. PS-b-PHEMA-b-PSSA triblock copolymer at 20:10:70 wt% was sequentially synthesized via atom transfer radical polymerization (ATRP). The middle block was crosslinked by sulfosuccinic acid (SA) via the esterification reaction between -OH of PHEMA and -COOH of SA, as demonstrated by FTIR spectroscopy. As increasing amounts of SA, ion exchange capacity (IEC) continuously increased from 2.13 to 2.82 meq/g but water uptake decreased from 181.8 to 82.7%, resulting from the competitive effect between crosslinked structure and the increasing concentration of sulfonic acid group. A maximum proton conductivity of crosslinked triblock copolymer membrane at room temperature reached up to 0.198 S/cm at 3.8 w% of SA, which was more than two-fold higher than that of Nafion 117(0.08 S/cm). Transmission electron microscopy (TEM) analysis clearly showed that the PS-b-PHEMA-b-PSSA triblock copolymer is microphase-separated with a nanometer range and well developed to provide the connectivity of ionic PSSA domains. The membranes exhibited the good thermal properties up to $250^{\circ}C$ presumably resulting from the microphase-separated and crosslinked structure of the membranes, as revealed by thermal gravimetric analysis (TGA).

• Macromolecular Research
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• v.9 no.4
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• pp.185-196
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• 2001

The self-assembly of block copolymers can lead to a variety of ordered structures on a nanometer scale. In this article, the self-assembling behaviors of triblock copolymers in the melt and the selective solvent are described with the results obtained from the computer simulations. With the advances of computing power, computer simulations using molecular dynamics and Monte Carlo techniques make it possible to study very complicated phenomena observed in the self-assembly of triblock copolymer. 13king full advantage of the computer simulation based on well-defined model, the effects of various structural and thermodynamic parameters such as the copolymer composition, the block sequence, the pairwise interaction energies, and temperature on the self-assembly are discussed in some detail. Some simulation results are compared with experimental ones End analyzed by comparing them with the theoretical treatment.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.326-326
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• 2006

The combination of living anionic and coordination polymerization techniques enabled to synthesize the polystyrene-b-polyisoprene-b-poly (butyl isocyanate) triblock polymers. Their microphase-separated structures were zig-zag structures for high ${\phi}_{PIC}$ samples, and hockey-puck structures were also observed. The phase diagram for PSt-b-PIp-b-PIC rod-coil polymers was different from that for PS-PBd-PMMA triblock polymers, and it was found that ${\phi}_{PIC}$ was the important factor to determine the microphase-separated structures.

• Macromolecular Research
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• v.9 no.2
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• pp.84-91
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• 2001

Both A-B-A triblock and multiblock copoly(ester-ether)s consisting of poly(L-Lactide) and poly(oxyethylene-co-oxypropylene) were prepared and characterized. The preparation of the triblock copolymer was done by ring-opening copolymerization of L-lactide with a commercially available telechelic copolyether, Pluronic$\^$TM/(PN) by catalysis of stannous octanoate. The molecular weight and unit composition of the produced copolymers were successfully controlled by changing the L-lactide/PN ratio in feed. However, a high molecular weight copolymer incorporating PN in large amount was not obtained because the molecular weight of the resulting copolymer was limited at a high L-lactide/PN composition. The multiblock copolymer was synthesized by the copolycondensation of oligo(L-lactic acid) prepared by thermal dehydration of L-lactic acid, PN, and dodecanedioic acid as carboxyl/hydroxyl adjusting agent. This polycondensation proceeded by catalysis of stannous oxide to give multiblock copolymers with high molecular weight and wide range of compositions.

• Macromolecular Research
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• v.13 no.6
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• pp.529-532
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• 2005

A novel amphiphilic, symmetric rod-coil, triblock copolymer (denoted as PHEMA-b-PF-b-PHEMA) of poly(9,9-didodecylfluorene-2,7-diyl) (PF) and poly(hydroxyl ethyl methacrylate) (PHEMA) was synthesized. A $\pi$-conjugated poly(9,9-didodecylfluorene-2,7-diyl) (PF) was used as a rodlike midblock segment and connected with hydrophilic end blocks of poly(hydroxyl ethyl methacrylate) (PHEMA) by using an ATRP technique. The chemical structure of PHEMA-b-PF-b-PHEMA was confirmed by $^{1}H$-NMR and GPC, and its PL properties were investigated in selected solvents. Due to the dissimilarities in molecular conformation and solubility between PHEMA and PF blocks, both block segments were segregated to display a phase-separated morphology on a Si wafer.

• Macromolecular Research
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• v.16 no.7
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• pp.609-613
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• 2008

Poly($\varepsilon$-caprolactone)-poly(ethylene glycol)-poly($\varepsilon$-caprolactone) (PCL-PEG-PCL) multiblock copolymers at various hydrophobic-hydrophilic ratios were successfully synthesized by the chain extension of triblock copolymers through isocyanate (hexamethylene diisocyanate). Biodegradable films were prepared from the resulting multiblock copolymers using the casting method. The mechanical properties of the films were improved by chain extension of the triblock copolymers, whereas the films prepared by the triblock copolymers were weak and brittle. Atomic force microscopy (AFM) of the multiblock copolymer film showed that the hydrophilic PEG had segregated on the film surface. This is consistent with the observed contact angle of the films.

• Macromolecular Research
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• v.10 no.6
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• pp.359-364
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• 2002

A series of PLA-PEO-PLA triblock stereo-copolymers with varying PLA/PEO and L-DL-LA ratios were synthesized via ring opening pelymerizations. Aqueous solutions of these copolymers undergo thermo-responsive phase transitions as the temperature monotonically increases. Further study shows that there is a critical gel concentration (CGC), and also lower and upper critical gel temperatures (CGTs), at which the thermo-responsive phase transition occurs. The CGC and CGTs are affected by various factors such as block length, as well as the compositions of the PLA blocks and of the additives. In particular, the changes in the phase diagram produced by varying the L-/DL-LA ratio in the PLA blocks were determined to be mainly due to consequent stereo-regularity changes in the PLA blocks.

• Proceedings of the PSK Conference
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• 2002.10a
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• pp.408.2-409
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• 2002

The aim of this study is to prepare biodegradable microspheres without use of any kind of surfactants or emulsifiers for a novel sustained delivery carriers of protein drugs. Poly(e-caprolactone)/poly(ethylene glycol)/poly(e-caprolactone) (CEC) triblock copolymer was synthesized by ring-opening of e-caprolactone with dihydroxy poly(ethylene glycol) and was used to make surfactant-free microspheres. (omitted)

• Elastomers and Composites
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• v.35 no.2
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• pp.106-114
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• 2000

The foam of ethylene vinyl acetate (EVA)/styrene-vinyl isoprene-styrene triblock copolymer(SVIS) blend was prepared to improve the shock-absorption and compression set characteristics at room temperature. The effects of blowing agent and blend ratio of EVA/SVIS on expansion ratio, cell structure and mechanical properties of the foam were investigated. As the SVIS content increased, the viscosity of blends was increased but the crosslinking rate was slow down, the expansion ratio was decreased. and the specific gravity was increased. At room temperature, the resilience was not affected by increasing the amount of blowing agent. The value of tan ${\delta}$ was increased by increasing the amount of SVIS. As a result, the value of compression set was decreased. This is due to the increased values of specific gravity and crosslinking density of the EVA/SVIS foam.