• Fibers and Polymers
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• 제3권1호
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• pp.8-13
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• 2002

The effect of block sequence on the self-assembly of ABC-type triblock copolymers in the ordered state is investigated using an isothermal-isobaric molecular dynamics simulation. The block sequence has an important effect ,on the ]norphology of ABC triblock copolymers. Different morphologies are observed depending on the block sequence as well as the block composition. The triblock copolymers with the volume fraction of 1 : 1 : 1 ($f_A$=$f_B$=$f_C$= 0.33) show the three phase and four layered lamellar structures irrespective of the block sequence. The $A_{32}$$B_{16}$$C_{32}$triblock copolymer with $f_B$=0.2 shows a morphology In which cylinders of midblock B are formed at the interface between A and C lamellae, whereas the morphology of triblock copolymer $B_{16}$$C_{32}$ $A_{32}$ and $C_{32}$ $A_{32}$ $B_{16}$ show a cylindrical core-shell structure and a lamellar type morphology, respectively. The $A_{20}$$B_{40}$$C_{20}$the triblock copolymer with the block B as a major component shows a tricontinuous structure, whereas both $B_{40}$$C_{20}$$A_{20}$ and $C_{20}$$A_{20}$$B_{40}$ triblock coolymers exhibit the lamellar structures. When the block B has larger volrome fraction with $f_B$=0.75, the matrix is composed of block B, and other two blocks A and C form spherical domains.

• Fibers and Polymers
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• 제4권1호
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• pp.15-19
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• 2003

The self-assembly of asymmetric ABC triblock copolymers in the ordered structure is investigated using an isothermal-isobaric molecular dynamics simulation. Unlike symmetric A BC triblock copolymers, more fascinating mophologies are observed in asymmetric ones because of a larger difference of incompatibility between the components. Various modes of self-assembly in assymmetric ABC triblock copolymers are also observed depending on the block composition. When the composition of block A Is changed from 0.125: to 0.25 at the same $f_B$ : 0.25, the morphological transition from the “cylinder in cylinder” to “cylinders at cylinder” structure is observed in the simulation. In the case of ABC triblocks with $f_B$=0.5, a lamellar-type structure is changed to a cylinder-type structure with increasing the length of block A. When the midblock length increases further to $f_B$=0.625, the “spheres on cylinder” structure is observed in both the $A_{10}$$B_{50}$$C_{20}$ and $A_{20}$$B_{50}$$C_{10}$ triblocks. From these results, the phase diagram of ABC triblock copolymers can be constructed.

• Macromolecular Research
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• 제17권5호
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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).

• 폴리머
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• 제33권5호
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• pp.458-462
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• 2009

본 연구에서는 순차적 음이온 및 개환중합반응을 통해 ABC 형태의 폴리스티렌-폴리에틸렌옥사이드-폴리락티드 블록공중합체를 성공적으로 합성하였다. 우선, 첫번째 블록인 폴리스티렌을 합성하기 위해서, 사이클로헥산 용매에서 스티렌/이차-부틸리튬을 각각 단량체/개시제로 사용하여 음이온중합(anionic polymerization)을 수행하였고, 이후 고분자 말단을 수산기로 전환시키기 위해, 에틸렌옥사이드를 첨가하였다. 다음 단계로 포타슘 나프탈레나이드(potassium naphthalenide)를 이용하여 폴리스티렌 말단 수산기의 수소를 제거하여, 거대개시제인 PS-$O^-K^+$를 제조하였다. 준비된 거대 개시제에 정량된 에틸렌옥사이드를 첨가하여, 음이온중합을 수행하였다. 폴리락티드 블록을 도입시키는 개환중합의 경우, THF 용매에서 트리에틸알루미늄(triethylaluminum)/피리딘(pyridine)시스템을 이용하여 PS-b-PEO-$AlEt_2$ 형태의 거대개시제를 형성한 후, $90^{\circ}C$에서 중합을 수행하였다. 합성된 블록공중합체를 수소핵자기공명법 및 겔침투크로마토그래피 방법을 통해 조사한 결과, 잘 정의된 분자량 및 낮은 분자량 분포를 나타냄을 확인할 수 있었다.