• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.297-297
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• 2006

Recently columnar liquid crystals have been studied due to their possible application to organic conducting materials. Supramolecular columnar liquid crystals consist of mesogenic unit which can aggregate into discs that will make up the columns which associate to form a two-dimensional network. In this study, we prepared supramolecular columnar liquid crystals containing hydrogen bonding between carboxylic acid and, pyridine moieties. Thermal and structural properties of prepared complexe were investigated, and it exhibited hexagonal columnar structure ($Col_{h}$) at room temperature.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.189-193
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• 1991

A series of compounds that contain varying numbers of the same mesogenic structure, biphenyl p-oxybenzoate unit, attached through a pentamethylene spacer to the central benzene ring were prepared and their liquid crystallinity was studied. The mesophase-forming ability of a dimesogenic compound was found to be greatly dependent on whether or not its geometric shape is linear and also on the existence of the pentamethylene spacer between the mesogen and the central core. The presence of the spacer enhanced the capacity of a compound to form a mesophase. In the trimesogenic compound the mesogens were linked to the 1,3,5-positions of the core benzene ring through the spacer. The compound was found to be enantiotropically nematic.

• Textile Coloration and Finishing
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• v.8 no.1
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• pp.56-63
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• 1996

A number of thermotropic liquid crystalline polyurethanes with mesogenic unit were synthesized by polyaddition of a para-type diisocyanate such as 1, 4-phenylene diisocyanate(1,4-PDI) with 4, 4'-bis($\omega$-hydorxyalkoxy) biphenyls($BP{m}$) in DMF. The thermal and liquid crystab line properties were examined by differential scanning calorimetry(DSC), polarized optical microscopy, and wide-angle X-ray scattering(WAXS). Intrinsic viscosities of the polymers exbibited two endothermic peaks correspondinding to phase transitions of melting and isotropization. For example, polyurethane(1,4-PDI/($BP{11}$) ) was found to display a liquid crystalline phase between 177 to 205$^{\circ}C$. In order to know how the hydrogen bonding interaction affects the formation of mesophases in polyurethane 1, 4-PDI/($BP{8}$) / thermal processing FT-IR measurements were carried out. It was found that the stretches regarded as shift to higher frequency region with increasing temperature which showed grdually their liquid crystalline phase

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.39-43
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• 2006

The relaxed torsional potential of a liquid crystalline polymer containing an ester functional group in a mesogenic unit (hereafter 12-4 oligomer) has been calculated with the ab initio self-consistent-field using 6-31G$^*$ basis set. GIAO^{13}C NMR chemical shifts also have been calculated at the B3LYP/6-31G$^*$ level of theory for each conformational structure obtained from torsional potential calculation. The results show that the phenyl ring-ester linkages are coplanar with the dihedral angle of about 0$^{\circ}$ and the ring-ring linkages in the biphenyl groups are tilted with the dihedral angle of around 43-44$^{\circ}$ in the lowest energy conformer. The biphenyl ring has a comparatively lower energy barrier of internal rotation potential in the ring-ring than that of phenyl ring-ester. The ^{13}C chemical shifts of carbonyl carbons were found to move to upfield due to $\pi$ -conjugation with phenyl ring and slightly affected about 0.5 ppm by dihedral angle of the ring-ring linkage.

• Textile Coloration and Finishing
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• v.7 no.4
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• pp.8-15
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• 1995

A series of thermotropic Polyurethanes mesogenic unit were synthesized by polyaddition of a para-type diisocyanate such as 2,5-tolylene diisocyanate(2,5-TDI) with 4-4'-bis($\omega$-hydroxyalkoxy) biphenls(BPm: $HOCmH_{2m}OC_{6}H_{4}OC_{m}H_{2m}OH$ : m is the carbon number of the hydroxyalkoxy group) in DMF. Intrinsic viscosities of the polymers were in the range of 0.41~0.99dL/g DSC thermograms for these polymers exhibited two endothermic peaks corresponding to phase transitions of melting and isotropization. For examplem polyurethane 2,5-TDI/BPll with [η]=0.99 prepared from 2.5-TDI and 4,4'-bis[11-hydroxyundecaoxy biphenyl(BP11) a liquid crystalline phase from 156 to 173$^{\circ}C$. The thermotropic properites of liquid crystalline polyurethanes have been investigated by wide-angle X-ray scatter(WAXS), infrared (IR) spectroscopy, and differential scanning calorimetry (DSC). The mesomorphic behavior of the polyurethanes was concluded to be greatly dependent on the intermolecular hydrogen bonds through the urethane.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.615-620
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• 2010

In this study, five series of novel polyurethanes was synthesized by the polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate(2,6-TDI), 2,5-tolylene diisocyanate(2,5-TDI), 2,4-tolylene diisocyanate(2,4-TDI), and 1,4-phenylene diisocyanate(1,4-PDI), hexamethylene diisocyanate(HDI) with 4,4'-Bis(3-hydroxypropoxy)biphenyl (BP3), 4,4'-bis(3-hydroxypropoxy)biphenyl exhibited a smectic type mesophase. Monotropic mesophase was found for all synthesized liquid crystalline polyurethanes except HDI/BP3. In contrast, 1,4-PDI/BP3 without a methyl substituent in the phenylene unit exhibited no explicit mesomorphic behavior, which was confirmed by DSC and polarizing microscopy experiments. Structures of the compound were identified by FT-IR and $^1H$-NMR spectroscopies. Their phase transition temperatures and thermal stability were also investigated by differential scanning calorimetry(DSC), polarized optical microscopy(POM) and x-ray diffraction analysis.

• Elastomers and Composites
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• v.48 no.4
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• pp.306-311
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• 2013

A series of liquid crystalline polyesters containing the 4-chloro benzoate group on the hydroquinone unit of rigid group were synthesized through solution polymerization of 2,5-di(4-chlorobenzoate)hydroquinones and 4,4'-dicarboxy-${\alpha},{\omega}$-diphenoxy alkane. The structure and properties for synthesized polymers were investigated by $^1H$-NMR, FT-IR, DSC, TGA, and POM. As result of investigations, The presence of the methylene group and bulky lateral groups in polymer chain have a great influence on the properties of polymers such as solubilities and thermal transitions. The optical textures of polymers revealed a weak birefringence in the melt and indicated that they form nematic mesophase. All polymers have very narrow mesophase temperature ranges.

• Polymer(Korea)
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• v.31 no.1
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• pp.58-67
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• 2007

Fully cholesteryloxycarbonated and (8-cholesteryloxycarbonyl) heptanoated disaccharide derivatives were synthesized by reacting cellobiose, maltose, and lactose with cholesteryl chloroformate or 8- cholesteryloxycarbonylheptanoyl chloride, and their thermotropic liquid crystalline properties were investigated. All the cholesteryloxycarbonated derivatives (CH1DSs) formed enantiotropic cholesteric phases, whereas all the (8-cholesteryloxycarbonyl) heptanoated derivatives (CH8DSs) exhibited monotropic cholesteric phases with left-handed helicoidal structures whose optical pitches (${\lambda}m's$) decrease with increasing temperature. All the CH1DSs, contrast with the CH8DSs, did not display reflection colors over the full cholesteric range, suggesting that the helicoidal twisting power of the cholesteryl group highly depends on the length of the spacer joining the cholesteryl group to the disaccharide chain. The thermal stability and degree of order in the mesophase and the temperature dependence of the ${\lambda}m$ observed for EH8DSs were entirely different from those reported for the cholesterol-bearing dimers and triplet and the (8-cholesteryloxycarbonyl) heptanoated polysaccharide derivatives. The results were discussed in terms of the difference in the number of the mesogenic units per mole of repeating unit and the flexibility of the main chain.

• Polymer(Korea)
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• v.34 no.2
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• pp.116-125
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• 2010

The thermotropic liquid crystalline behavior of the homologous series of combined-type liquid crystalline polymers, tri-O-{4-(4'-cyanophenylazo)phenoxy}alkyl celluloses (CACETn, where n, the number of methylene units in the spacer, is 2~10) have been investigated. The CACETn with n of 5 and 7 exhibited enantiotropic nematic phases, while other polymers showed monotropic nematic phases. The isotropic-nematic transition temperature($T_{iN}$) increased when n is increased up to 4, but it decreased with increasing n more than 5. The entropy change at $T_{iN}$ also reaches a minimum at n=5, before it increases again for n=6. The sharp change at n=5 may be attributed to the difference in arrangement in the side groups. The nematic-crystalline transition temperatures, in contrast with $T_{iNS}$, exhibited a distinct odd-even effect, suggesting that the average shape of the side chains in the crystalline phase is different from that in the nematic phase. The mesophase properties of CACETn were significantly different from those reported for tri-O-alkyl celluloses and poly[1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s. The results were discussed in terms of the difference in the chemical structures of the main and side chains and the number of the mesogenic units per repeating unit.

• Polymer(Korea)
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• v.33 no.1
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• pp.58-66
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• 2009

The thermotropic liquid crystalline behavior of the homologous series of cellulose tri[4-{4'-(nitrophenylazo) phenoxycarbonyl}] alkanoates (NACEn, n=2$\sim$8, 10, the number of methylene units in the spacer) have been investigated. All of the homologoues formed monotropic nematic phases. The isotropic-nematic transition temperature ($T_{iN}$) decreased when n is increased up to 7, but it became almost constant when n is more than 7. The plot of transition entropy at $T_{iN}$ against n had a sharp negative inflection at n=7. The sharp change at n=7 may be attributed to the difference in arrangement of the side groups. The melting temperature ($T_m$) and associated entropy change at $T_m$, in contrast with $T_{iN}$ and associated entropy change at $T_{iN}$, exhibited a distinct odd-even effect, suggesting that the average shape of the side chains in the crystalline phase is different from that in the nematic phase. The thermal stability and degree of order of the nematic phase observed for NACEn were significantly different from those reported for the homologous series of side-chain and combined type liquid crystal polymers bearing azobenzene or biphenyl units in the side chains. The results were discussed in terms of the differences in the chemical structure, the flexibility of the main chain, the mode of chemical linkage of the side group with the main chain, and the number of the mesogenic units per repeating unit.