• Title/Summary/Keyword: Triblock copolymer

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Preparation and Reconstitution of Core-shell Type Nanoparticles of Poly(ε -caprolactone)/Poly(ethyleneglycol)/Poly(ε -caprolactone) Triblock Copolymers

  • Jeong, Young-Il;Ryu, Jae-Gon;Kim, Young-Hoon;Kim, Sung-Ho
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.872-879
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    • 2002
  • One of the improtant characteristics of core-shell type nanoparticles is the long-term storage and reuse as an aqueous injection solution when required. For this reason, reconstruction of lyophilized core-shell type nanoparticles is considered to be essential . BAB type triblock copolymers differ from AB type diblock copolymers, which contain the A block as a hydrophilic part and the B block as a hydrophobic part. by not being easily redistributed into phosphate-buffered saline (PBS, pH 7.4, 0.1 M). Therefore, lyophilized core-shell type nanoparticles of CEC triblock copolymer were reconstituted using a somication process with a bar-type sonicator in combination with a freezing-thawing process. Soncation for 30s only resuspended CEC nanoparticles in PBS; their particle size distribution showed a monomodal pattern with narrow size distribution. The bimodal size distribution pattern and the aggregates were reduced by further sonication for 120 s but these nanoparticles showed a wide size distribution. The initial burst of drug release was increased by reconstitution process. The reconstitution of CEC core-shell type nanoparticles by freezing-thawing resulted in trimodal distribution pattern and formed aggregates, although freezing-thawing process was easier than sonication . Drug release form CEC nanoparticles prepared by freezing-thawing was slower than from the original dialysis solution. Although core-shell typenanoparticles of CEC triblock copolymers were not easily performed. Cytotoxicity testing of core-shell type nanoparticles of CEC-2 triblock copolymers containing clonazepam (CNZ) was performed using L929 cells. Cytotoxicity of CNZ was decreased by incorporation into nanoparticles.

In vitro Biodegradability and Surface Properties of Block Copoly(ester-ether)s Consisting of Poly(L-lactide) and Polyether

  • Lee, Chan-Woo;Kim, Yoshiharu ura
    • Macromolecular Research
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    • v.11 no.1
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    • pp.42-46
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    • 2003
  • Cell attachment and proliferation on the polymer films of triblock copolymer(ester-ether)s comprising po1y (L-1actide) (PLLA) and poly (oxyethylene-co-oxypropylene)(PN) were investigated using 3T3 fibroblasts. It was found that on the tissue culture polystyrene(TCPS) and the PLLA control film the cells could spread well while on the copolymer films the cells showed a rounded morphology without spreading and proliferated weakly. Especially, little cells proliferated on the films of copolymer having a LN composition of 20 wt%. While the water absorption of the copolymer films increased with increasing PN content, the contact angle against water of copolymer films immersed in aqueous medium was almost identical, being slightly lower than that of the PLLA film. These properties were compatible with the results of cell attachment. The in vitro hydrolysis of the films of triblock and multiblock type copolymers was faster with increasing PN content. The increased hydrolyzability, the flexibility and the decreased cell attachment suggested that these copolymers may have high potential as biodegradable materials for medical use.

Foaming Characteristics of Ethylene Vinyl Acetate/Styrene Vinyl Isoprene Styrene Triblock Copolymer Blend (Ethylene Vinyl Acetate / Styrene Vinyl Isoprene Styrene Triblock Copolymer 블렌드의 발포특성)

  • Heo, Jae-Young;Kim, Jin-Tae;Yoon, Jung-Sik;Yoo, Jong-Sun;Kim, Won-Ho
    • 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.

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Polymer Electrolyte Membranes of Poly(Styrene-Butadiene-Styrene) Star Triblock Copolymer for Fuel Cell (연료전지용 Poly(Styrene-Butadiene-Styrene) Star Triblock Copolymer의 고분자 전해질 분리막)

  • Garcia, Edwin D.;Jung, Bumsuk
    • Membrane Journal
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    • v.29 no.5
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    • pp.252-262
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    • 2019
  • A sulfonated star branched poly(styrene-b-butadiene-b-styrene) triblock copolymer (SSBS) was synthesized with varying degrees of sulfonation. The effective sulfonation on the butadiene block was confirmed by FT-IR spectroscopy. Ion exchange capacity by titration was used to determine the degree of sulfonation. The synthesized polymer observed enhanced water uptake and proton conductivity. At room temperature, the SSBS with 25 mol% degree of sulfonation showed an outstanding proton conductivity of 0.114 S/cm, similar to that of commercial membrane, Nafion. The effect of temperature at constant relative humidity on conductivity resulted to a remarkable increase in proton conductivity. Methanol permeability studies showed a value lower than Nafion for all the sulfonated membranes. Structural nature observed using AFM showed that the membranes observed microphase separated nanostructures and the connectivity of the interionic channels.

Synthesis and Characterization of Di and Triblock Copolymers Containing a Naphthalene Unit for Polymer Electrolyte Membranes (고분자전해질 막을 위한 나프탈렌 단위를 포함하는 디 및 트리 블록공중합체의 합성 및 특성분석)

  • KIM, AERHAN
    • Transactions of the Korean hydrogen and new energy society
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    • v.27 no.6
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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.

Novel pH/Temperature Sensitive Hydrogels of Poly (ethylene glycol)-Poly (caprolactone) -Poly (${\beta}-amino\;ester$) (PAE-PCLA-PEGPCLA-PAE) Biodegradable Polyester Block Copolymer

  • Huynh Dai Phu;Lee Doo-Sung
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.263-263
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    • 2006
  • Poly (ethylene glycol)(PEG) - Poly (${\varepsilon}-caprolactone(CL)$) - Poly (D,L lactide(LA) (PCLA-PEG-PCLA) was synthesized by ring-opening polymerization to form temperature sensitive hydrogel triblock copolymer. The triblock copolymer was acrylated by acryloyl chloride. ${\beta}-amino$ ester was used as a pH sensitive moiety, in this study ${\beta}$- amino ester obtained from 1,4-butandiol diacrylate, and 4, 4' trimethylene dipiperidine, it have pKb around 6.6. pH/temperature sensitive penta-block copolymer (PAE-PCL-PEG-PCL-PAE) was synthesized by addition polymerization from acrylated triblock copolymer, 1,4-butandiol diacrylate, and 4, 4' trimethylene dipiperidine. Their physicochemical properties of triblock and penta-block copolymers were characterized by $^1H-NMR$ spectroscopy and gel permeation spectroscopy. Sol-gel phase transition behavior of PAE-PCL-PEG-PCL-PAE block copolymers were investigated by remains stable method. Aqueous media of the penta-block copolymer (at 20 wt%) changed from a sol phase at pH 6.4 and $10^{\circ}C$ to a gel phase at pH 7.4 and $37^{\circ}C$. The sol-gel transition properties of these block copolymers are influenced by the hydrophobic/hydrophilic balance of the copolymers, block length, hydrophobicity, stereo-regularity of the hydrophobic of the block copolymer, and the ionization of the pH function groups in the copolymer depended on the changing of environmental pH, respectively. The degradation and the stabilization at pH 7.4 and $37^{\circ}C$, and the stabilization at pH 6.4 and $10^{\circ}C,\;5^{\circ}C,\;0^{\circ}C$, of the gel were determined. The results of toxicity experiment show that the penta block copolymer can be used for injection drug delivery system. The sol?gel transition of this block copolymer also study by in vitro test ($200{\mu}l$ aqueous solution at 20wt% polymer was injected to mouse). Insulin loading and releasing by in vitro test was investigated, the results showed that insulin can loading easily into polymer matrix and release time is around 14-16days. The PAE-PCL-PEG-PCL-PAE can be used as biomaterial for drug, protein, gene loading and delivery.

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Thermally Induced Mesophase Development in Ethanesilica Films via Macromolecular Templating Approach

  • Cho, Whirang;Char, Kook-Heon;Kwon, Su-Yong
    • Macromolecular Research
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    • v.17 no.9
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    • pp.697-702
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    • 2009
  • Mesoporous ethanesilica thin film was prepared using PEO-PLGA-PEO triblock copolymers as structure-directing agents and (1,2-bis(triethoxysilyl) ethane BTESE; bridged organosilicates) as inorganic precursors via one-step sol-gel condensation of ethanesilica precursors. The mesostructure of ethanesilica films is critically dependent on the processing experimental parameters after the hydrolyzed silica sol mixture was spin-cast. This study examined the effects of the block copolymer template/organosilica precursor ratio in the casting solution and aging period before calcination of the mesostructure. It was further demonstrated that mesoscopic ordering of organosilicate thin films is induced by the rearrangement of block copolymer template/organosilica hybrid during thermal decomposition of the PEO-PLGA-PEO triblock copolymer. The mesoporous structure and morphology were characterized by SAXS, TEM and solid-state NMR measurement.

Proton Conducting Crosslinked Membranes by Polymer Blending of Triblock Copolymer and Poly(vinyl alcohol)

  • Lee, Do-Kyoung;Park, Jung-Tae;Choi, Jin-Kyu;Roh, Dong-Kyu;Lee, Jung-Hyun;Shul, Yong-Gun;Kim, Jong-Hak
    • Macromolecular Research
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    • v.16 no.6
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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.

Self-Assembly of Triblock Copolymers in Melts and Solutions

  • Kim, Seung-Hyun;Jo, Won-Ho
    • 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.

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