• Journal of the Korean Applied Science and Technology
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• v.14 no.3
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• pp.55-61
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• 1997

Maxwell displacement current(MDC) measuring technique has been applied on the study of monolayers of polyamic acid containing p-cyanoazobenzene. The displacement current was generated from monolayers on the water surface by monolayer compression and expansion. Displacement current was generated when the area per molecule was about $140{\AA}^2$ and $100{\AA}^2$. Maxwell displacement currents were investigated in connection with monolayer compression cycles. It was found that the maximum of MDC appeared at the molecular area just before the initial rise of surface pressure in compression cycles.

• Korean Journal of Optics and Photonics
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• v.10 no.5
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• pp.386-390
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• 1999

Erasable polarization holographic grating was recorded with two-wave mixing in PCN which was side-chain liquid crystalline polymalonic esters containing two symmetrical 4-cyanoazobenzene as photoresponsive groups. The diffraction efficiency of recorded grating was measured and the characteristics of recording, decay in a dark room and erasing by circularly polarized light were investigated. As the results, birefringence, $\Delta$n of PCN was measured $6.5{\times}10^{-2}$, which was 0~100 times higher than those of crystals such as Fe:$LiNbO_3$, Ce:$BaTiO_3$ crystals. Dark decay rates was $4.3{\times}10^{-5}$ %/hour, which showed the possibility of application as data storage media.

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1421-1427
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• 1999

4-Hydroxy-4'-methoxyazobenzene and 4-hydroxy-4'-cyanoazobenzene were synthesized from phenol with p-anisidine and p-aminobenzonitrile through a diazotization reaction, respectively. They were reacted with 2-chloroethanol, 2-(2-chloroethoxy)ethanol, or 2-[2-(2-chloroethoxy)ethoxy]ethanol to produce six kinds of new mesogenic alcohols having an azobenzene group that is sensitive to the ultraviolet. Twelve kinds of new photoresponsive monomers with two symmetrical mesogens were prepared by the reaction of the mesogenic alcohols with fumaric acid or maleic acid through a Mitsunobu reaction. The resulting monomers have different length of flexible ethyleneoxy spacer tethered to azobenzene group. The length of the spacer affected their thermal stability, solubility, and phase transition temperature. Structures of the monomers were identified by FT-IR and ¹H-NMR spectra. Their phase transition temperatures and thermal stability were also investigated by a differential scanning calorimetry (DSC) and a thermogravimetric analysis (TGA). From an optical polarizing microscopy, all the prepared monomers except fumarate-1 and maleate-1 were found to show enantiotropic liquid crystallinity with a smectic texture like focal-conic, fan-shaped, and batonnet textures.

• Polymer(Korea)
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• v.36 no.1
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• pp.76-87
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• 2012

Three kinds of hydroxypropyl cellulose (HPC) derivatives, [6-{4-(4-cyanophenylazo)phenoxy}]hexyloxypropyl celluloses (CAHPCs) with degree of etherification (DET) ranging from 0.4 to 3, fully substituted acrylic acid esters of HPC (HPCA) and CAHPCs (CAHPCAs) were synthesized. The crosslinked HPCA (HPCAG) and CAHPCAs (CAHPCAGs) were also prepared by exposing thermotropic mesophases of HPCA and CAHPCAs to UV light. Both CAHPCs and CAHPCAs with DET ${\leq}$ 1.2, as well as HPC and HPCA, formed enantiotropic cholesteric phases whose optical pitches(${\lambda}_m$'s) increase with temperature, wheras both CAHPCs and CAHPCAs with DET ${\geq}$ 1.4 showed monotropic nematic phases. CAHPCAGs with DET ${\leq}$ 1.2, as well as CAHPCAs with DET ${\leq}$ 1.2, exhibited reflection colors in a wide temperature range. On the other hand, CAHPCAGs with DET ${\geq}$ 1.4, as well as CAHPCAs with DET ${\geq}$ 1.4, showed Schileren textures typical of nematic phase, indicating that the liquid crystalline structure is virtually locked upon photocrosslinking. The isotropization temperatures($T_i$'s) of both CAHPCAs and CAHPCAGs decreased with increasing DET. The $T_i$ of CAHPCAG, however, was higher than that of CAHPCA at the same DET. Moreover, the temperature dependence of ${\lambda}_m$ of CAHPCAGs was much weaker than that of CAHPCAs.

• 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.

• 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.

• 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.

• Applied Chemistry for Engineering
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• v.20 no.6
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• pp.603-611
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• 2009

Thermotropic liquid crystalline behavior of a homologous series of penta-O-4-{4'-(cyanophenylazo)phenoxy}alkyl-D-glucopyranoses(CAGETn, n = 2~10, the number of methylene units in the spacer) has been investigated. The CAGETn with n of 2 and 7 exhibited enantiotropic nematic phases whereas other derivatives showed monotropic nematic phases. This is the first report of glucose derivatives that form thermotropic nematic phases. The isotropic-nematic transition temperatures ($T_{iNS}$) of CAGETns and their entropy variation at $T_{iN}$ showed the odd-even effect as a function of n. This behavior was rationalized in terms of the change in the average shape of the side chains as the parity of the spacer is varied. This rationalization also accounts for the observed variation of nematic-crystalline phase transition temperatures ($T_{NkS}$) and associoated entropy change at $T_{Nk}$. The entropy change at $T_{iN}$ or $T_{Nk}$ reaches a mininum at n = 3, before it increases again for n = 4. This may be attributed to the difference in the arrangement of the side groups. The mesophase properties of CAGETns were entirely different from those reported for partially or fully alkylated glucopyranoses. This result suggests that the degree of substitution and chemical structure of the substituents play an important role in the formation of the mesophase structures in the liquid crystals.

• Polymer(Korea)
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• v.33 no.4
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• pp.297-306
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• 2009

A homologous series of side chain liquid crystalline polymers, poly [1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s(CAPETn, where n, the number of methylene units in the spacer, is $2{\sim}10$) were synthesized from poly(vinyl alcohol) and 1-{4-(4'-cyanophenylazo)phenoxy}alkylbromides(CAPBn, n=$2{\sim}10$), and their thermotropic liquid crystalline phase behaviors were investigated. The CAPBn with n of $2{\sim}5$ did not show any liquid crystalline behavior, while those with n of 6 and $7{\sim}10$ showed enantiotropic and monotropic nematic phases, respectively. In contrast, among the CAPETn polymers, only CAPET5 exhibited an enantiotropic nematic phase, while other polymers showed monotropic nematic phases. The isotropic-nematic transition temperatures of CAPETns and their entropy variation at the phase transition that were higher values than those of CAPBns, demonstrated a typical odd-even effect as a function of n. These phase transition behaviors were disscussed in terms of the 'virtual trimer model' by Imrie. The mesophase properties of CAPETns were largely different from those reported for the polymers in which the (cyanophenylazo) phenoxy groups are attached to polyacrylate, polymethacrylate, and polystyrene backbones through polymethylene spacers. The results indicate that the mode of chemical linkage of the side group with the main chain plays an important role in the formation, stabilization, and type of mesophase.