• Polymer(Korea)
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• v.29 no.6
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• pp.523-535
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• 2005

Linear aromatic polyesters are representative examples of thermotropic liquid crystalline polymers (TLCPs), which have been the subject of many researches. This article reviews the structure-LC properties relationship in wholly aromatic CLCPs mostly based on the results obtained for the past quarter of a century. Especially, this review deals with the structural details of aromatic polyester TLCPs that influence the liquid crystalline and thermal properties. In the last part of this article the liquid crystalline properties of combined type and hyperbranched polyester also are discussed. Introduction to various synthetic methods are included in the last section.

• Bulletin of the Korean Chemical Society
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• v.21 no.10
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• pp.1031-1034
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• 2000

• Analytical Science and Technology
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• v.8 no.4
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• pp.493-498
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• 1995

PAZO-6 is a new combined type liquid crystalline polymers (LCP) which has two types of mesogens combined non linearly. Ordering of branch mesogen azo group, in PAZO-6 is an important parameter to observe as well as the substitution effect on the backbone. The related small molecules sllch as monomers as well as the polymer itself are studied by solid state NMR techniques. Preliminary $^{13}C$ CP/MAS (cross polarization/ magic angle spinning) spectral results suggest that the azo groups in the monomers are not aligned with themselves. Azo groups in the monomers seem to be poorly ordered between well ordered p-phenylene terephthalate moeities. Similar disordering tendency of the azo group in PAZO-6 is deduced from the overall aromatic carbon peak positions which are not much different from those of the monomer.

• Polymer(Korea)
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• v.31 no.1
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• pp.37-46
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• 2007

Fully or nearly fully 6- [4- (4'- (nitrophenylazo)phenoxycarbonyl)]pentanoated polysaccharide derivatives were synthesized by reacting cellulose, amylose, chitosan, chitin, alginic acid, pullulan or amylopectin with 6- [4- (4'- (nitrophenylazo)phenoxy) ] pentanoyl chloride (NA6C) and their thermotropic liquid crystalline behaviors were investigated. Like in the case of NA6C, all the polysaccharide derivatives formed monotropic nematic phases, suggesting that the mesophase structure of the polysaccharide derivatives is dertermined by the mesogenic side groups and not by the polysaccharide backbone. This is the first report of polysaccharide derivatives, except cellulose derivative, that form thermotropic nematic phases. The thermal stability and degree of order of the nematic phases observed for poly saccharide derivatives were significantly different from those reported for the polymers in which the azobenzene groups are attached to flexible or rigid backbones through flexible spacers. The results were discussed in terms of the difference in the arrangement of the main and side chains 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.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.178-183
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• 1998

Carbon-13 CP-MAS NMR techniques were used to investigate dynamics of new combined type liquid crystalline polymers, poly[oxy-1,4-phenyleneoxy-2-{6-(4-(4-butylphenylazo)phenoxy)hexyloxy}terephthaloyl] and poly[oxy-1,4-phenyleneoxy-2-{10-(4-(4-butylphenylazo)phenoxy)decyloxy}terephthaloyl]. Noticeable mobility change of either aromatic groups or methylene groups is not detected between 25 ℃ and 82 ℃ from 13C spinlattice relaxation time in the rotating frame (T1ρ(C)) and contact time array experiments. However, line shape analysis shows the increase of mobility of methylene carbons in poly[oxy-1,4-phenyleneoxy-2-{6-(4-(4-butylphenylazo)phenoxy)hexyloxy}terephthaloyl] at higher temperature. The dynamics of side chanis does not seem to be affected in our experimental temperature range by the length of aliphatic chain which is connecting the side chain group to the main chain.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.24 no.3
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• pp.111-119
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• 2014

A novel pulsed laser ablation process in liquid was investigated to prepare scheelite-type ceramic [calcium tungstate ($CaWO_4$) and calcium molybdate ($CaMoO_4$)] nanocolloidal particles. The crystalline phase, particle morphology, particle size distribution, absorbance and optical band-gap were investigated. Stable colloidal suspensions consisting of well-dispersed $CaWO_4$ and $CaMoO_4$ nanoparticles with narrow size distribution could be obtained without any surfactant. Particle tracking analysis using optical microscope combined with image analysis was applied for a fast determination of particle size distribution in the prepared nanocolloidal suspensions. The mean nanoparticle size of $CaWO_4$ and $CaMoO_4$ colloidal nanoparticles were 16 nm and 30 nm, with the standard deviations of 2.1 and 5.2 nm, respectively. The optical absorption edges showed blue-shifted values about 60~70 nm than those of reported in bulk crystals. And also, the estimated optical energy band-gaps of $CaWO_4$ and $CaMoO_4$ colloidal particles were 5.2 and 4.7 eV. The observed band-gap widening and blue-shift of the optical absorbance could be ascribed to the quantum confinement effect due to the very small size of the $CaWO_4$ and $CaMoO_4$ nanocolloidal particles prepared by pulsed laser ablation in liquid.

• Polymer(Korea)
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• v.30 no.4
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• pp.338-349
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• 2006

Fully or nearly fully(8-cholesteryloxycarbonyl)heptanoated polysaccharide derivatives were synthesized by reacting cellulose, amylose, chitosan, chitin, alginic acid, pullulan or amylopectin with (8-cholesteryloxycarbonyl)heptanoyl chloride (CH8C), and their thermotropic liquid crystalline behaviors were investigated. Like in the case of CH8C, all the polysaccharide derivatives formed monotropic cholesteric phases with left-handed helicoidal structures whose optical pitches $({\lambda_m}'s)$ decrease with increasing temperature. Amylopectin derivative also formed a monotropic cholesteric phase with lefthanded helicoidal structures but, in contrast with the other derivatives, did not display reflection colors over the full cholesteric range, suggesting that the helicoidal twisting power of the cholesteryl group highly depends on the branched structure in amylopectin. The thermal stability and degree of order in the mesophase, the magnitude of ${\lambda}_m$ at the same temperature, and the temperature dependence of the ${\lambda}_m$ observed for polysaccharide derivatives were entirely different from those reported for the polymers in which the cholesteryl groups are attached to flexible or semiflexible backbones through flexible spacers. The results were discussed in terms of the difference in the chemical structures of the main and side chains and flexibility of the main chain.

• 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.