• Macromolecular Research
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• v.15 no.5
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• pp.437-442
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• 2007

Poly(ethylene glycol) methyl ether (PEG)-poly(${\beta}$-amino ester) (PAE) block copolymers were synthesized using a Michael-type step polymerization, and the construction of pH-sensitive polymeric micelles (PM) investigated. The ${\beta}$-amino ester block of the block copolymers functioned as a pH-sensitive moiety as well as a hydrophobic block in relation to the ionization of PAE, while PEG acted as a hydrophilic block, regardless of ionization. The synthesized polymers were characterized using $^1H-NMR$, with their molecular weights measured using gel permeation chromatography. The $pK_b$ values of the pH-sensitive polymers were measured using a titration method. The pH-sensitivity and critical micelle concentration (CMC) of the block copolymers in PBS solution were estimated using fluorescence spectroscopy. The pH dependent micellization behaviors with various bisacrylate esters varied within a narrow pH range. The critical micelle concentration at pH 7.4 decreased from 0.032 to 0.004 mg/mL on increasing the number of methyl group in the bisacrylate from 4 to 10. Also, the particle size of the block copolymer micelles was determined using dynamic light scattering (DLS). The DLS results revealed the micelles had an average size below 100 nm. These pH-sensitive polymeric micelles may be good carriers for the delivery of an anticancer drug.

• Polymer(Korea)
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• v.35 no.3
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• pp.223-227
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• 2011

Stimuli-responsive polymers have been investigated as the materials playing the critical roles in various applications. Thermoresponsive graft copolymers, poly (N-isopropylacrylamide)-g-hyaluronic acid (PNIPAAm-g-HA) and elastin-like peptide-g-hyaluronic acid (ELP-g-HA), were synthesized by coupling carboxylic polymers (PNIPAAm-COOH or ELP) to biocompatible HA through amide linkages. Thermoresponsive behavior was observed in both the copolymers, and the results of turbidity measurement were consistent with the results of rheological examination. Among the two copolymers, the ELP graft copolymer shows less cooperative LCST transition than the PNIPAAm case. As the content of graft chains of PNIPAAm and ELP increases, viscosity increases, and the increase was larger in PNIPAAm case at a graft content. These results shows us that the introduction of grafts provides thermosensitivity to biocompatible HA, whose characteristics can be engineered.

• Bulletin of the Korean Chemical Society
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• v.8 no.2
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• pp.96-101
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• 1987

2-Ethoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyran (1_a$), 2-n-butoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyr an (1b), 2-isobutoxy-6-methoxy-5-cyano-3,4-dihydro-2H-py ran ($1_c$), and 2-ethoxy-6-methoxy-3-methyl-5-cyano-3,4-dihydro -2H-pyran ($1_d$) were prepared by (4 + 2) cycloaddition reaction of methyl $\alpha$-cyanoacrylate with the corresponding alkyl vinyl ethers. Compounds $1_{a-d}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, head-to-tail (H-T) copolymer $3_a$ was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $1_H% NMR and IR spectra, but in the $^{13}C$ NMR spectra significant differences were observed between the H-H and H-T copolymers. Glass transition temperature ($T_g$) of H-H copolymer was higher than that of the H-T copolymer, but thermal decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. Compounds $1_a$, $a_b$, and $1_c$, copolymerized well with styrene by cationic catalyst, but compound 1d failed to copolymerize with styrene. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.4 dl/g.

• 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.

• Polymer(Korea)
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• v.38 no.1
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• pp.9-15
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• 2014

Polyamide4 (PA4)-polyurethane (PU)-PA4 triblock copolymers were synthesized by isocynated (NCO)-terminated PU prepared from 4,4'-diphenyl methane diisocyante (MDI) and polytetramethylene glycol (PTMG) as an initiator and potassium pyrrolidonate (P-py) as a catalyst for anionic ring opening polymerization of 2-pyrrolidone. Subsequently copolymer was controlled to contain different or same molecular weight of PA4 hard block with same or different molecular weight of PU soft block in order to investigate the effects of those differences on various properties of triblock copolymers as a thermoplastic elastomer. As the results shown in typical properties of block copolymeric elastomers, the mechanical strength and melting point ($T_m$) of the copolymers increased with an increase in molecular weight of PA4 block while the elongation at break increased with an increase in that of PU block.

• Proceedings of the KIEE Conference
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• 1999.07d
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• pp.1563-1565
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• 1999

Linear and nonliear complex permittivities have been measured for amorphous copolymers of vinylidene cyanide (VDCN) with vinyl acetate (VAc), vinyl propionate (VPr), vinyl benzoate (VBz), styrene (St) and methyl methacrylate (MMA). It is found that the third order permittivity ${\varepsilon}_3$ depends upon frequency according to a function ${\Delta}_{{\varepsilon}_3}/(1+i{\omega}{\tau}_^3)$ while the linear permittivity obeys a Debye function ${\Delta}_{{\varepsilon}_1}/(1+i{\omega}{\tau}_1)$. Experimental results are well fitted by the above predicted functions except at low frequencies where dc conduction dominates. The ${\tau}_1$ and ${\tau}_3$ are nearly equal, and depend upon temperature according to a WLF form. The relaxation strength ${\Delta}_{{\varepsilon}_1}$ depends upon comonomers ranging from $130_{{\varepsilon}_0}$(VAc) to $20{{\varepsilon}_0}$(MMA). The ${\Delta}_{{\varepsilon}_3}$ is negative and depends more strongly upon comonomers. Combined knowledge about linear and nonlinear permittivities predicts very large correlation factors which indicates strongly cooperative dipolar motions in those amorphous copolymers.

• Polymer(Korea)
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• v.32 no.2
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• pp.95-102
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• 2008

The $\alpha$,$omega$-diacrylate poly(dimethylsiloxane) (DA-PDMS) containing vinyl ester of versatic acid/vinyl acetate (Veova-10/VAc) was prepared by emulsion copolymerization of (DA-PDMS), Veova-10 (with VAc), and auxiliary agents at $85^{\circ}C$ in the presence of ammonium peroxodisulfate (APS) as an initiator. Sodium dodecyl sulfate (SDS) and nonylphenol ethylene oxide-40 units (NP-40) were used as anionic and nonionic emulsifiers, respectively. The resulting copolymers were characterized by using Fourier transform infrared spectroscopy (FT-IR). Thermal properties of the copolymers were studied by using thermogravimetric analysis(TGA) and differential scanning calorimetry (DSC). The morphology of copolymers was also investigated by scanning electron microscopy (SEM) and then the effects of variables such as temperature, agitation speed, surfactant kinds, molecular weights, initiator, and DA-PDMS concentrations on the properties of the silicone-containing Veova-10/VAc emulsions were examined. The calculation of monomer conversion versus time histories indicates that by increasing the DA-PDMS concentration the polymerization rate and the number of polymer particles decrease, respectively.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1029-1036
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• 2012

Push-pull-type copolymers - low-band-gap copolymers of electron-rich fused-ring units (such as cyclopentadithiophene; CPDT) and electron-deficient units (such as benzothiadiazole; BT) - are promising donor materials for organic solar cells. Following a design principles proposed in our previous study, we investigate the electronic structure of a series of new CPDTBT derivatives with various electron-withdrawing groups using the time-dependent density functional theory and predict their power conversion efficiency from a newlydeveloped protocol using the Scharber diagram. Significantly improved efficiencies are expected for derivatives with carbonyl [C=O], carbonothioyl [C=S], dicyano [$C(CN)_2$] and dicyanomethylene [C=$C(CN)_2$] groups, but these polymers with no long alkyl side chain attached to them are likely to be insoluble in most organic solvents and inapplicable to low-cost solution processes. We thus devise several approaches to attach alkyl side chains to these polymers while keeping their high efficiencies.

• Journal of Environmental Science International
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• v.15 no.6
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• pp.593-600
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• 2006

SIS triblock copolymers, one of the major raw materials of oil gelling agent, were synthesized by living anionic polymerization and the resultant copolymers formed with various shapes and sizes were used to examine their oil gelling capacities. Coupling method was adapted to form final triblock products from diblock living polymers. Prior to polymerization, the impurities in monomers and solvents were throughly removed by killing technique. We experimentally investigated the effects of operating parameters of synthesis and forming of SIS triblock copolymers on oil gelling capacity. The photocatalytic decomposition of SIS triblock copolymer under ultraviolet circumstance was also investigated and it is found that the addition of P-25 enhances the photocatalytic decomposition.

• Journal of Korea Foresty Energy
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• v.18 no.2
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• pp.55-61
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• 1999

This study was carried out to investigate the influence of viscoelastic properties(or chemical composition) of a series of ethylen-viny1 acetate copolymers on impact noise and vibration damping of wood/polymer/wood sandwich composites. The impact noise and vibration damping of composites were very sensitive to the state of molecular motion of polymer. The noise and vibration damping of composites were maximum when the polymer was under the glass transition(vinylacetate 55~75%) at the test-temperature, and minimum rubbery state(vinyl-acetate 47~20%) or glassy state(vinylacetate 100~87%). The polymer under glass transition reduced the impact noise by 6~12 dB.