• Polymer(Korea)
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• v.28 no.1
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• pp.92-102
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• 2004

(6-Cholesteryloxycarbonylpentoxypropyl)celluloses (CHPCs) with degree of esterification (DE) ranging from 2.25 to 2.91 were synthesized by reacting hydroxypropyl cellulose with 6-cholesteryloxycarbonylpentanoyl chloride. The acrylic esters of CHPCs (CHPCEs) and their photocrosslinked films with liquidcrystalline order were also synthesized. The thermotropic properties of mesophase for both uncrosslinked and crosslinked samples and the swelling behavior of the crosslinked samples in acetone were investigated. The hydroxypropyl cellulose exhibited an enantiotropic cholesteric phas, while all the uncrosslinked cholesterylbearing samples exhibited a monotropic cholesteric phases; the 6-cholesteryloxycarbonylpentanoyl chloride also showed a monotropic smectic phase. The hydroxypropyl cellulose formed a right-handed helix whose optical pitch (λ$\sub$m/) increases with temperature, whereas all the uncrosslinked derivatives farmed left-handed helices whose λ$\sub$m/'s decreased with temperature. The thermal stability of the mesophase and the magnitude of λ$\sub$m/ at the same temperature for both CHPCs and CHPCEs decreased with increasing DE. All the crosslinked samples, in constrast with CHPCEs, did not display reflection colors but exhibited an anisotropic swelling characteristic of crosslinked gel retaining liquid-crystalline order.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.20 no.4
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• pp.86-92
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• 2019

Polymers with various compositions of azobenzene and hexamethylene groups in the main chain were synthesized by a Schotten-Baumann reaction and their properties were investigated. The chemical structures and physical properties of the synthesized polymers were investigated by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, differential scanning calorimetry, thermogravimetric analysis, polarized optical microscopy, and x-ray diffraction. The polymers showed an inherent viscosity of 1.28-1.36 dl/g and were relatively insoluble in most organic solvents. The melt transition temperature increased rapidly with increasing number of azobenzene groups in the polymer. When the azobenzene monomer content was more than 50 mol%, no melting transition occurred below the decomposition temperature. Among the polymers with a melt transition temperature, the MP-A3C7 and MP-A5C5 polymers were liquid crystalline materials and exhibited a nematic phase with weak liquid crystallinity over a wide liquid crystal temperature range. This difference in the properties of the synthesized polymers is likely due to the changes in intermolecular forces resulting from the linearity and polarity of the trans-form of azobenzene.

• Macromolecular Research
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• v.12 no.2
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• pp.156-171
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• 2004

We describe the precision synthesis schemes of siloxane-containing polymers, i.e., the control of their molecular weight, stereoregularity, and higher-order structures. First, we found a new catalytic dehydrocoupling reaction of water with bis(dimethylsilyl)benzene to give poly(phenylene-disiloxane). Together with this reaction, we applied hetero-condensations to the synthesis of thermally stable poly(arylene-siloxane)s. The dehydrocoupling reaction was applied to the synthesis of syndiotactic poly(methylphenylsiloxane) and poly(silsesquioxane)s, which we also prepared by hydrolysis and deaminative condensation reactions. We discuss the tendency for loop formation to occur in the synthesis of poly(silsesquioxane) by hydrolysis, and provide comments on the design of functionality of the polymers produced. By taking advantage of the low energy barrier to rotation in the silicon-oxygen bond, we designed selective oxygen-permeable membrane materials and liquid crystalline materials. The low surface free energy of siloxane-containing systems allows surface modification of a blend film and the design of holographic grating materials.

• Composites Research
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• v.12 no.6
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• pp.53-64
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• 1999

Microstructural morphology and bending strengths of moulded composites of thermotropic liquid crystalline polymer(LCP) and polyamide 6 (PA6) have been studied as a function of epoxy fraction. Injection-moulding of a composite plaque at a temperature below the melting point of the LCP fibrils generated a multi-layered structure: the surface skin layer with thickness of $65\;-\;120{\mu\textrm{m}}$ exhibiting a transverse orientation; the sub-skin layer with an orientation in the flow direction; the core layer with arc-curved flow patterns. The plaques containing epoxy 4.8vol% exhibited superior bending strength and large fracture strain. With an increase of epoxy fraction equal to and beyond 4.8vol%, geometry of LCP domains was changed from fibrillar shape to lamella-like one, which caused a shear-mode fracture. An analysis of the bending strength of the composite plaques by using a symmetric layered model beam suggested that addition of epoxy component altered not only the microstructural geometry but also the elastic moduli and strengths of the respective layers.

• Polymer(Korea)
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• v.36 no.6
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• pp.776-788
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• 2012

Octa[8-{4-(4'-cyanophenylazo)phenoxy}]octyl and octa[8-{4-(4'-cyanophenylazo)phenoxycarbonyl}]heptanoated disaccharide derivatives were synthesized by reacting cellobiose, maltose, and lactose with 1-{4-(4'-cyanophenylazo) phenoxy}octylbromide or 1-{4-(4'-cyanophenylazo)phenoxycarbonyl}]heptanoyl chloride, and their thermotropic liquid crystalline and photochemical phase transition behavior were investigated. All the {(cyanophenylazo)phenoxy} octyl disaccharide ethers (CADETs) formed monotropic nematic (N) phases, whereas all the {(cyanophenylazo) phenoxycarbonyl}heptanoated disaccharide esters (CADESs) exhibited enantiotropic N phases. Compared with CADETs, CADESs showed higher isotropic (I)-to-N phase transition temperatures. Photoirradiation of the disaccharide derivatives in a glass cell or in a cell with a rubbed polyimide (PI) alignment layer at a N phase resulted in disappearance of the N phase due to trans-cis photoisomerization of azobenzene, and the initial N phase was recovered when the irradiated sample was kept in the dark because of cis-trans thermal isomerization and reorientation of trans-azobenzenes. The rates of the photochemical N-I and the thermal I-N phase transition of disaccharide derivatives in a cell with a rubbed PI alignment layer were faster than those in a glass cell, and were significantly different from those observed for the monomesogenic compounds containing cyanoazobenzene and the 4-{4'-(cyanophenylazo)phenoxy}octyl glucose and cellulose ethers. The results were discussed in terms of difference in cooperative motion of azobenzene groups due to the flexibility of the main chain, the number of mesogenic units per repeating units, and the distance between the azobenzene groups.

• Journal of the Korean Electrochemical Society
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• v.11 no.2
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• pp.120-124
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• 2008

Carbon-coated $LiFePO_4$ and $LiMn_{0.4}Fe_{0.6}PO_4$ cathode materials for lithium batteries were synthesized by a sol-gel method. X-ray diffraction and scanning electron microscopy data showed that the cathode materials are pure crystalline and are surrounded by porous carbon. The initial discharge capacities of $LiFePO_4$ and $LiMn_{0.4}Fe_{0.6}PO_4$ with the liquid electrolyte of 1M $LiPF_6$ in EC/DMC are 132 mAh/g and 145 mAh/g, respectively, at current density of 0.1 C-rate. $LiFePO_4$ and $LiMn_{0.4}Fe_{0.6}PO_4$ with an electrospun polymer-based electrolyte exhibit initial discharge capacities of 114 and 130 mAh/g at 0.1 C-rate at room temperature, respectively.

• Polymer(Korea)
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• v.34 no.1
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• pp.32-37
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• 2010

Photo-alignment property of groove patterned surface prepared from blend of poly (vinyl cinnamate) (PVCi) and oligomeric dicinnamate was investigated for the application for alignment layer of liquid crystal display. The study of the photoreaction kinetics using UV-vis spectrum with the irradiation time showed that the reaction rate of oligomeric cinnamate was enhanced compared to that of PVCi. Blend where PVCi was main component showed a slight improvement on the photoreaction rate. It was unable to obtain groove patterned surface only using oligomeric cinnamate itself owing to the high crystalline character. However, blending of PVCi made it possible to obtain clear surface pattern. Molecular orientation could be confirmed from the polar plot data. It can be suggested that blend of oligomeric cinnamate and polymeric cinnamate is promising material for the photoalignment layer.

• Applied Chemistry for Engineering
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• v.18 no.5
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• pp.475-482
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• 2007

The thermal and optical properties of glucose penta(cholesteryloxycarbonyl)alkanoates (CAGLn, n = 2~8, 10, the number of methylene units in the spacer) were investigated. All the CAGLn formed monotropic cholesteric phases with left-handed helical structures. CAGLn with n = 2 or 10, in contrast with CAGLn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer joining the cholesteryl group to the glucose chain. The isotropic-cholesteric transition point ($T_{ic}$) decreased with increasing n and showed no odd-even effect. The plot of transition entropy at $T_{ic}$ against n had a sharp negative inflection at n = 7. The optical pitches (${{\lambda}_m}^{\prime}$ s) of CAGLn with $3{\leq}n{\leq}8$ decreased with increasing temperature. However, the temperature dependence of the ${\lambda}_m$ of the derivatives exhibited pronounced dependence on n. The transitional properties and the temperature dependence of the ${\lambda}_m$ observed for CAGLn were discussed in terms of the differences in arrangement of the cholesteryl groups and the conformation of the molecules.

• Polymer(Korea)
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• v.33 no.3
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• pp.254-262
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• 2009

Nine kinds of hydroxypropyl celluloses (HPCs) with degree of substitution (DS) and molar substitution (MS) ranging from 2.10 to 2.71 and 2.3 to 6.7, respectively and seven kinds of fully butanoated HPCs (BPCs) based on the HPCs with $2.3\;{\le}\;MS\;{\le}\;6.7$ were synthesized, and the molecular characteristics of HPCs and the thermotropic liquid crystalline properties of the derivatives were investigated. MS was nearly equal to DS for small value of DS, but it became exceedly larger than DS for $DS{\gtrsim}1$, showing that in the later stages of reaction, propylene oxide preferentially adds to the side chains rather than the main chain. All the derivatives formed enantiotropic cholesteric phases with right-handed helical structures. The glass and clearing transition temperatures of both HPCs and BPCs were decreased with increasing MS. The optical pitches (${\lambda}_m'S$) of BPCs, as well as HPCs themselves, increased with increasing temperature. However, the ${\lambda}_m'S$ of both HPCs and BPCs at the same temperature increased with increasing MS. Moreover, the temperature dependence of ${\lambda}_m$ of HPCs was weaker than that of BPCs, suggesting that the helical twisting power of the cellulose chain highly depends on the length and chemical structure of the side chain introduced in cellulose chain.