• Fibers and Polymers
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• v.1 no.1
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• pp.12-17
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• 2000

Thermotropic polyurethanes were synthesized from 1,6-hexane diisocyanate (HDI) as a diisocyanate, 1,6-hexane diol (HD), and rigid diols containing imide unit such as N,N＇-bis(4-hydroxyphenyl)-3,4,3＇,4＇-biphenyl-dicarboxyimide (BPDI) or bis-N-(4-hydroxyphenyl)-4,4＇-oxydiphthalimide (ODPI). The effects of structure difference between BPDI and ODPI and composition of HD/BPDl (ODPI) on the thermal and liquid crystalline behavior were studied. Thermotropic polyurethanes with an inherent viscosity of 0.59~0.70 were obtained. The melting temperature of BPDI-based polyurethanes were in the range of 150~$290^{\circ}C$, however, those of ODPI-based polyurethanes were in the range of 150~$190^{\circ}C$. All the polyurethanes based on ODPI (25~100 mole %) clearly exhibited a stable liquid crystalline phase, and BPDI-based polyurethane having 5-25% of BPDT showed a mesophase. The melting and isotropization temperatures ($T_m$, $T_i$) and ΔT($T_i$ - $T_m$) increased with increasing BPDI and ODPI content. The polyurethanes based on BPDI has higher melting points and thermal stability compared to ODPI-based polyurethanes.

• 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.

• Textile Coloration and Finishing
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• v.2 no.4
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• pp.237-244
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• 1990

Syntheses and liquid-Crystallinites of thermotropic copoly (ester amide)s were investigated. The three components melt polycondensation of 4,4'-dicarboxy-$\alpha$, $\omega$-diphenoxyalkane as an A component, 4-4'diacetoxybiphenyl as a B, and p-N-acetoxy-aminobenzoic acid as a C gave the thrmotropic copoly(ester amide)s containing a flexible splacer in the polymer backbone. Diacetylated hydroquinone, methyl hydroquinone, chlorohydroquinone, and phenyl hydroquinone were used as anther B components. A polymer(6BPAB) having 10 mol% of C component and hexamethylene space. showed a typical nematic texture between $245^{\circ}C(T_m)\; and\; more\; than\; 360^{\circ]C(T_i)$. The melting points of the members of this series of polymers increased with decreasing methylene spacer. The polymer structure and mesomorphic nature were examined by solid and solution ^{13}C-NMR4 spectroscopy, cross polarizing microscopy with a hot stage, and X-ray diffactometry.

• Textile Coloration and Finishing
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• v.5 no.2
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• pp.109-116
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• 1993

Synthesis and liquid-crystallinites of thermotropic polyamides and copolyamides were investigated. Thermotropic polyamides and copolyamides containing a flexible spacer in the backbone were obtained by the two or three components melt polycondensations of 4,4'-dicarboxy-${\alpha}$${\omega}$-diphenoxy alkane as an A components, 4,4'-diacetoamido-3,3' dimethoxybiphenyl as a B, 1,4-diacetoamido-benzene (diacetylated p-phenylenediamine) was used as another amide-group-forming minomer. The content of the amide groups in the thermotropic polyamide and Copolyamide widely varied depending on the structure of the amide-group forming diacetoamido monomers. A polymer (9CLDI) showed a typical nematic texture between 218$^{circle}C$ ($T_m$) and 345$^{circle}C$($T_i$) The melting points of the members of this series of polymers increased with decreasing methylene spacer. The polymer structure and mesmorphic nature were examined by solid and solution ${^13}C$-NMR spectroscopy, cross polarizing microscopy with a hot stage.

• 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.

• Macromolecular Research
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• v.14 no.3
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• pp.383-386
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• 2006

High temperature size exclusion chromatography (SEC) has been used widely for the characterization of crystalline polymers, for which high temperature operation above the polymer melting temperature is required to dissolve the polymers. However, this high temperature operation has many advantages in SEC separation in addition to merely increasing polymer solubility. At high temperature the eluent viscosity decreases, which in turn decreases the column backpressure and increases the diffusivity of the analytes. Therefore, many reports on the high temperature operation of high performance liquid chromatography (HPLC) have focused on shortening the analysis time and enhancing the resolution. However, the application of high temperature SEC analysis to exploit the merits of high temperature operation is scarce. In this article, therefore, we report on a new apparatus design for high temperature SEC.

• Applied Chemistry for Engineering
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• v.22 no.4
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• pp.358-366
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• 2011

A homologous series of linear liquid crystal dimers, the ${\alpha},{\omega}$-bis(4-cyano-azobenzene-4'-oxy)alkanes (CATWETn, where n, the number of methylene units in the spacer, is 2~10) were synthesized, and their thermotropic liquid crystalline phase behavior were investigated. The CATWETn with n of 3 and 6 exhibited monotropic nematic phases, whereas other derivatives showed enantiotropic nematic phases. The nematic-isotropic transition temperatures of the dimers and their entropy variation at the phase transition showed a large odd-even effect as a function of n. This phase transition behavior was rationalized in terms of the change in the average shape of the spacer on varying the parity of the spacer. The thermal stability and degree of order in the nematic phase and the magnitude of the odd-even effect of CATWETn were similar to those for the methoxy-, nitro-, and pentyl-substituted dimers, while they were significantly different from those for the monomesogenic compounds, 1-{4-(4'-cyanophenylazo)phenoxy}alkylbromides and the side-chain liquid-crystalline polymers, the poly[1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s. The results were discussed in terms of 'virtual trimer model' by Imrie.

• Macromolecular Research
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• v.12 no.2
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• pp.195-205
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• 2004

We have synthesized new aromatic polyesters (DiPEG-HQ and DiPEG-BP) by condensation polymerization of a terephthalic acid derivative bearing a pendant oligo(oxyethylene) (DP = 7, MW = 350), which has a methoxy terminal group, and two different aromatic diols, hydroquinone and 4,4'-biphenoI. The synthesized polymers were characterized by differential scanning calorimetry (DSC), polarizing microscopy, and X-ray diffractometry for their liquid crystallinity (LC), thermal transitions, and structural morphologies in mesophases. The morphology of the LC phases depends strongly on the length of the rigid backbone repeating unit. The DiPEG-BP polymer having a longer repeating unit exhibits both layered and nematic structures before isotropization, whereas the DiPEG-HQ polymer having a shorter repeating unit shows only the layered structure in the mesophase. We found that the layer spacing for DiPEG-HQ is larger than that for DiPEG-BP. Both polymers easily form complexes with LiCF$_3$SO$_3$; we studied this complex formation by FT-IR spectroscopy. The layer spacing of the polymer-electrolyte composites increases upon increasing the amount of the lithium salt. The polymer/salt electrolyte mixtures we investigated at molar ratios of EO:salt in the range of 5-20 exhibit electrical conductivity values at 40$^{\circ}C$ of 2.4${\times}$10$\^$5/ and 1.1${\times}$10$\^$－5/ S/cm for DiPEG-HQ/LiCF$_3$SO$_3$ and DiPEG-BP/LiCF$_3$SO$_3$, respectively. At 80 $^{\circ}C$, these values are higher: 4.6${\times}$10$\^$－3/ and 1.1${\times}$10$\^$－4/ S/cm, respectively. The activation energy of conductivity depends strongly on the salt concentration.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.169-169
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• 2006

Novel liquid crystalline malonic ester monomers were synthesized from malonyl dichloride and mesogenic alcohols as a photoresponsive group. The monomers were polymerized with aliphatic or aromatic dibromides in the presence of sodium hydride to give 8 kinds of novel poly(malonic esters) with two symmetrical azobenzene groups. We found that the resulting polymer films could be used as rewritable optical data storage (or holographic image) media through a photoisomerization of azobenzene group by Ar laser irradiation. The sensitivity of data recording was dependent not only on the thickness of the polymeric thin film but also on the intensity of laser beam.

• Proceedings of the Korean Fiber Society Conference
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• 1998.04a
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• pp.28-31
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• 1998

Photoresponsive polymers are being intensely investigated over last two decades, which can be attributed to both fundamental and applied significance. Presently the attention is being directed to these materials in view of their possible application in nonlinear optics and optoelectronics. It was demnstrated quite early that by covalent fixation of both photochromic group and the mesogenic group to the same polymer main chain high concentration of photochromic group can be attained.(omitted)