• 제목/요약/키워드: 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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    • 제23권6호
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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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    • 제11권1호
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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.

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

  • 허재영;김진태;윤정식;유종선;김원호
    • Elastomers and Composites
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    • 제35권2호
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    • pp.106-114
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    • 2000
  • 상온에서의 충격 흡수특성과 compression set 특성을 향상시키기 위하여 ethylene vinyl acetate copolymer (EVA)와 styrene vinyl isoprene styrene triblock copolymer (SVIS)를 블렌드하여 발포체를 제조하였다. 발포제 및 EVA/SVIS 블렌드비가 발포배율 및 기계적 물성에 미치는 영향을 조사하였다. SVIS 함량이 증가함에 따라 블렌드의 점도는 증가하였고 가교 속도는 감소하였으며, 발포배율은 감소하여 비중은 증가하였다. 발포제 함량 증가, 즉 발포배율 증가에 따른 반발탄성은 변화가 없는 반면에, SVIS 함량 증가에 따라 발포체의 상온에서의 tan ${\delta}$ 값은 증가하였으며 따라서 반발 탄성은 감소함을 알 수 있었다. EVA/SVIS 블렌드 발포체에서 SVIS 함량 증가에 따라 가교밀도와 비중이 증가하므로 compression set 값도 낮은 값을 나타내었다.

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

  • 에드윈 가르시아;정범석
    • 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.

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

  • 김애란
    • 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.

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
    • 한국고분자학회:학술대회논문집
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    • 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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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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    • 제17권9호
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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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    • 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.

Self-Assembly of Triblock Copolymers in Melts and Solutions

  • Kim, Seung-Hyun;Jo, Won-Ho
    • Macromolecular Research
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    • 제9권4호
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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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