• Macromolecular Research
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• 제16권6호
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• pp.549-554
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• 2008

Proton conducting crosslinked membranes were prepared using polymer blends of polystyrene-b-poly(hydroxyethyl acrylate)-b-poly(styrene sulfonic acid) (PS-b-PHEA-b-PSSA) and poly(vinyl alcohol) (PVA). PS-b-PHEA-b-PSSA triblock copolymer at 28:21:51 wt% was synthesized sequentially using atom transfer radical polymerization (ATRP). FT-IR spectroscopy showed that after thermal ($120^{\circ}C$, 2 h) and chemical (sulfosuccinic acid, SA) treatments of the membranes, the middle PHEA block of the triblock copolymer was crosslinked with PVA through an esterification reaction between the -OH group of the membrane and the -COOH group of SA. The ion exchange capacity (IEC) decreased from 1.56 to 0.61 meq/g with increasing amount of PVA. Therefore, the proton conductivity at room temperature decreased from 0.044 to 0.018 S/cm. However, the introduction of PVA resulted in a decrease in water uptake from 87.0 to 44.3%, providing good mechanical properties applicable to the membrane electrode assembly (MEA) of fuel cells. Transmission electron microscopy (TEM) showed that the membrane was microphase-separated with a nanometer range with good connectivity of the $SO_3H$ ionic aggregates. The power density of a single $H_2/O_2$ fuel cell system using the membrane with 50 wt% PVA was $230\;mW/cm^2$ at $70^{\circ}C$ with a relative humidity of 100%. Thermogravimetric analysis (TGA) also showed a decrease in the thermal stability of the membranes with increasing PVA concentration.

• 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.

• 폴리머
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• 제38권1호
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• pp.9-15
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• 2014

Methylene diphenyl diisocyanate(MDI)와 poly(tetramethylene glycol)(PTMG)로부터 양말단에 isocyanate(NCO) 작용기를 가진 polyurethane(PU) prepolymer를 제조한 다음 이를 개시제로 하고 potassium pyrrolidonate를 촉매로 하여 2-pyrrolidone을 음이온 개환중합함으로써 최종적으로 양 끝에 polyamide4(PA4)가 단단한 블록이 되고 PU가 부드러운 블록이 되는 PA4-PU-PA4 형태의 삼블록 공중합체를 합성하였다. 그리고 공중합체내 각각 PA4 블록과 PU 블록의 분자량을 변화시켜 이들의 변화가 여러 가지 성질에 미치는 영향을 확인하였다. 결과적으로 PA4 블록으로 인해 원래의 PU 탄성체보다 용융온도($T_m$)는 크게 상승하였고 PA4 블록의 분자량이 증가함에 따라 초기 탄성률과 인장강도는 크게 증가하였다. 한편, PU 블록의 분자량이 증가되면 파단신율이 증가하였지만 초기 탄성률과 인장강도는 감소하는 전형적인 블록 공중합체형 탄성체의 성질을 나타냈다.

• 멤브레인
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• 제29권5호
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• pp.252-262
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• 2019

서로 다른 술폰화 정도에 따라 sulfonated star branched poly(styrene-b-butadiene-b-styrene) triblock copolymer (SSBS)가 합성되었다. 술폰화된 butadiene block은 FT-IR spectroscopy로 확인할 수 있다. 술폰화 정도를 측정 비교하기 위해서 산-염기 적정을 통하여, ion exchange capacity (IEC)를 계산하였다. 술폰화된 SSEB 전해질막은 높은 water uptake와 proton conductivity를 보였다. 실온에서 25 mol% 술폰화된 SSBS는 0.114 S/cm라는 높은 값을 나타냈으며, 이는 Nafion과 비슷한 수치였다. 일정한 상대 습도에서 온도의 증가는 현저하게 높은 수소이온전도도를 나타냄을 알 수 있었다. 모든 술폰화된 막은 Nafion과 비교했을 때 낮은 methanol 투과도를 보여주었다. AFM을 이용하여 술폰화된 전해질막의 구조는 이른바 분리된 나노구조의 미세상과 ionic channel의 접속으로 이루어졌음을 확인할 수 있었다.

• 한국수소및신에너지학회논문집
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• 제27권6호
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• pp.660-669
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• 2016

A fluorinated-sulfonated, hydrophobic-hydrophilic copolymer was planed subsequently synthesized using typical nucleophilic substitution polycondensation reaction. A novel AB and ABA (or BAB) block copolymers were synthesized using sBCPSBP (sulfonated 4,4'-bis[4-chlorophenyl)sulfonyl]-1,1'-biphenyl), DHN (1,5-dihydroxynaphthalene), DFBP (decafluorobiphenyl) and HFIP (4,4'-hexafluoroisopropylidenediphenol). All block copolymers were easily cast and made into clear films. The structure and synthesized copolymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (Fourier transform infrared). TGA (Thermogravimetric analysis) and DSC (differential scanning calorimetry) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. Hydrophobic/hydrophilic phase separation and clear ionic aggregate block morpology was confirmed in both triblock and diblock copolymer in AFM (atomic force microscopy), which may be highly related to their proton transport ability. A sulfonated BAB triblock copolymer membrane with an ion-exchange capacity (IEC) of 0.6 meq/g has a maximum ion conductivity of 40.3 mS/cm at $90^{\circ}C$ and 100% relative humidity.

• Archives of Pharmacal Research
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• 제26권6호
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• pp.504-510
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• 2003

The aim of this study is to prepare biodegradable microspheres without the use of surfactants or emulsifiers for a novel sustained delivery carriers of protein drugs. A poly($\varepsilon$-caprolactone)/poly(ethylene glycol)/poly($\varepsilon$-caprolactone) (CEC) triblock copolymer was synthesized by the ring-opening of $\varepsilon$-caprolactone with dihydroxy poly (ethylene glycol) to prepare surfactant-free microspheres. When dichloromethane (DCM) or ethyl formate (EF) was used as a solvent, the formation of microspheres did not occur. Although the microspheres could be formed prior to lyophilization under certain conditions, the morphology of microspheres was not maintained during the filtration and lyophilization process. Surfactant-free microspheres were only formed when ethyl acetate (EA) was used as the organic solvent and showed good spherical micro-spheres although the surfaces appeared irregular. The content of the protein in the micro-sphere was lower than expected, probably because of the presence of water channels and pores. The protein release kinetics showed a burst release until 2 days and after that sustained release pattern was showed. Therefore, these observations indicated that the formation of microsphere without the use of surfactant is feasible, and, this the improved process, the protein is readily incorporated in the microsphere.

• Bulletin of the Korean Chemical Society
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• 제33권5호
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• pp.1638-1642
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• 2012

A series of poly (lactic acid) (PLA) and poly (ethylene glycol) (PEG) tri and multiblock copolymers with relatively high molecular weights were synthesized through the coupling reaction between the bis(acyl chloride) of carboxylated PLA and mono or dihydroxy PEG. The coupling reaction and the copolymer structures were monitored by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The melting temperature (Tm) of PEG blocks decreased with the presence of PLA sequences attaching to PEG blocks. The CMC values were determined to be 10-145 mg/L depending on the length of PLA and PEG blocks and the structure of the block copolymers.

• Macromolecular Research
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• 제17권5호
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• pp.313-318
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• 2009

The side chain liquid crystal triblock copolymers (TBCs), which underwent phase transitions below their decomposition temperature, were prepared by copolymerization of poly(n-butyl acrylate) and a comonomer containing the mesogenic azobenzene group. The physical properties of TBCs in the distinctive transition temperature ranges were investigated in terms of the liquid crystal (LC) content in the copolymers. The phase transition temperatures traced optically, thermally and rheologically were well coincided one another and clearly exhibited the phase transition of smectic-nematic-isotropic with increasing temperature. In the smectic phase, increasing temperature made the liquid crystal system more elastic, but viscosity (${\eta}'$) remained almost constant. In the nematic phase, increasing temperature abruptly decreased ${\eta}'$ and G', ultimately leading to isotropic phase. Both smectic and nematic phases exhibited Bingham viscosity behavior but the former gave much greater yield stress at the same LC content.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2002년도 봄 학술발표회 논문집
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• pp.352-354
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• 2002

A series of ABA type triblock copolymers of trimethylene carbonate (TMC) and $\varepsilon$-caprolactone($\varepsilon$-CL) with different molar ratio were synthesized using ethylene glycol as initiator and stannous octoate as catalyst by ring-opening bulk polymerization. The characterization of the triblock copolymers was characterized by $^1$H-NMR, $\^$13/C-NMR, FT-IR, GPC and DSC, and compared with random copolymer. (omitted)

• Macromolecular Research
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• 제10권2호
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• pp.54-59
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• 2002

ABA triblock copolymers of L-lactide and trimethylene carbonate with several different compositions were prepared by sequential ring-opening polymerization in the presence of diethylene glycol. Also chain-extension reactions of the resulting copolymers were carried out using hexamethylene diisocyanate to produce relatively high molecular weight polymers, which could be cast into elastomeric tough films. The polymers with certain L-lactide contents were partially crystalline, exhibiting two-phase morphology. The polymer films showed reversible elastic behavior under tensile tension, providing a novel thermoplastic elastomer possessing desirable properties such as biodegradability and good mechanical properties.