• 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.

• Journal of Welding and Joining
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• v.33 no.4
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• pp.44-49
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• 2015

The structural epoxy adhesive used in car body assembly needs the highest level of joint mechanical strength under lap shear, T-peel and impact peel conditions. In this study, the effect of nano functionalized block copolymer addition on the impact peel strength of epoxy adhesive was investigated. DSC analysis showed that the addition of nano functionalized block copolymer did not affect the curing reaction of epoxy adhesive. From single lap shear test, it was found out that the addition of nano functionalized block copolymer slightly decreased the cohesive strength of cured adhesive layer. The addition of nano functionalized block copolymer showed beneficial effect on T-peel strength by changing the adhesive failure mode to the mixed mode. However, the addition of nano functionalized block copolymer just decreased the room temperature impact peel strength. It was considered that the addition of nano functionalized block copolymer could have effect on disturbing the crack propagation only for the case of slow strain rate.

• Macromolecular Research
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• v.16 no.4
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• pp.267-292
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• 2008

Block copolymers that two or more polymer chains are covalently linked have drawn much attention due to self-assembly into nanometer-sized morphology such as lamellae, cylinders, spheres, and gyroids. In this article, we first summarize the phase behavior of block copolymers in bulk and thin films and some applications for new functional nanomaterials. Then, future perspectives on block copolymers are described.

• Macromolecular Research
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• v.17 no.6
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• pp.365-377
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• 2009

In this feature article, we briefly review the new methods we have utilized recently in the investigation of morphology and phase behavior of block copolymers. We first describe the chromatographic fractionation method to purify block copolymers from their side products of mainly homopolymers or block copolymer precursors inadvertently terminated upon addition of the next monomer in the sequential anionic polymerization. The chromatographic method is extended to the fractionation of the individual block of diblock copolymers which can yield the diblock copolymer fractions of different composition and molecular weight, which also have narrower distributions in both molecular weight and composition. A more detailed phase diagram could be constructed from the set of block copolymer fractions without the need of acquiring many block copolymers each prepared by anionic polymerization. The fractions with narrow distribution in both molecular weight and composition exhibit better long-range ordering and sharper phase transition. Next, epitaxial relationships between two ordered structures in block copolymer thin film is discussed. We employed the direct visualization method, transmission electron microtomography(TEMT) to scrutinize the grain boundary structure.

• Applied Chemistry for Engineering
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• v.29 no.4
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• pp.395-398
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• 2018

In this work, profound microscale behaviors of block copolymer and polymer blend under electric field were investigated using microscopic methods and compared systematically. To this end, both the block copolymer and blend containing polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) were introduced. The two polymers have a similar dielectric constant. Under an identical experimental condition such as temperature, film thickness, field intensity, and exposure time, the polymer blend responded more sensitively than the block copolymer. The presence of covalent bond suppressed the mobility of constituents in block copolymer. This study will be essential for future research activities regarding behaviors of polymeric materials under external fields.

• Journal of the Korean Applied Science and Technology
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• v.18 no.2
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• pp.118-126
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• 2001

Micelle formation and adsorption at the $Ti0_{2}$ interface of a series of polystyrene-polythylene oxide(PS-PEO) block copolymer in aqueous solution was studied using fluorescence probing and small-angle X-ray methods. Further, the stability of aqueous $Ti0_{2}$ dispersion in the presence of copolymer was investigated by microelectrophoresis, optical density and sedimentation measurements. The dissolution of pyrene as fluorescent probe in aqueous surfactant solution leads to a slow decrease of the $I_{1}/I_{3}$ ratio, as the copolymer concentration increase; $I_{1}$ and $I_{3}$ are respectively the intensities of the first and third vibrionic peaks in the pyrene fluorescence emission. The behaviour was due to the characteristics of the copolymers and/or to the copolymer association efficiency in water. Moreover, the adsorption at the plateau level increases with decreasing PEO until chain length. The zeta potential of $TiO_{2}$ particles decreases with increasing copolymer concentration and reaches a plateau value. Finally, stabilization using block copolymers was more effective with samples having higher weight fractions of PS block.

• Bulletin of the Korean Chemical Society
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• v.22 no.5
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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.

• Journal of Radiation Industry
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• v.6 no.2
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• pp.171-176
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• 2012

In this study, a crosslinked poly(styrene-butadiene-styrene) [SBS] block copolymers were prepared by using gamma ray irradiation method. The effects of various radiation doses on the degree of crosslinking, thermo property, and morphology of crosslinked SBS block copolymer were investigated. The degree of crosslinking of crosslinked SBS block copolymers were measured by gel-fraction and FT-IR. It was found that the degree of crosslinking of crosslinked SBS block copolymers increases with increase of the irradiation dose while the TGA result shows that the initial degradation temperature of irradiated SBS block copolymer was shifted to lower temperature with increasing irradiation dose. These results indicate that degradation reaction also occurs when SBS block copolymer is exposed to gamma ray irradiation for crosslinking reaction. The SAXS and FE-SEM results indicate that the phase separation of the styrene block and butadiene block was reduced with increasing irradiation dose.

• Journal of Pharmaceutical Investigation
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• v.22 no.4
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• pp.323-326
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• 1992

$Poly({\varepsilon}-carbobenzoxy\;L-lysine)/poly(ethylene oxide)/poly({\varepsilon}-carbobenzoxy\;L-lysine)$ (LEL) block copolymers containing $poly({\varepsilon}-carbobenzoxy\;L-lysine)$ (PCLL) as the A component and poly(ethylene oxide) (PEO) as the B component were investigated as drug delivery matrix. PCLL homopolymer and LEL block copolymer microspheres containing anticancer drug, cytarabine, were prepared by a solvent evaporation process and the release patterns of cytarabine from the microspheres were investigated in vitro. The size of PCLL homopolymer and LEL block copolymer microspheres was ranged from $0.2\;{\mu}m$ to $1\;{\mu}m$ in diameter and the shape of the microspheres was almost round. The release pattern of cytarabine from the block copolymer microspheres was dependent on the mole % of PEO of the block copolymers.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.6.2-6.2
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• 2011

Block copolymer (BCP) self-assembly in a film geometry has recently been the focus of increased research interest due to their potential use as templates and scaffolds for the fabrication of nanostructured materials. The phase behavior in a thin film geometry that confines polymer chains to the interfaces will be influenced by the interfacial interactions at substrate/polymer and polymer/air and the commensurability between the equilibrium period (L0) of the BCP and the total film thickness. We investigated the phase transitions for the films of block copolymers (BCPs) on the modified surface, like the order-to-disorder transition (ODT) by in-situ grazing incidence small angle x-ray scattering (GISAXS) and transmission electron microscopy (TEM). The selective interactions on the surface by a PS-grafted substrate provide the preferential interactions with the PS component of the block, while a random copolymer (PS-r-PMMA) grafted substrate do the balanced interfacial interactions on the surface. The thickness dependence of order-to-disorder behavior for BCP films will be discussed in terms of the surface interactions.