• Macromolecular Research
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• v.10 no.4
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• pp.230-235
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• 2002

Alternating polyols of oxymethylene and oxyalkylene were synthesized and used as precursors for thermoplastic poly(ether-ester) elastomers (TPEs). The polyols were synthesized by reacting diols having different methylene units with dichloromethane in the presence of a phase transfer catalyst. The number of methylene units in the alkylene oxides was varied from 3 to 6. TPEs were prepared using the polyols as soft segments and poly(butylene terephthalate) units as hard segments. The polyols and TPEs synthesized were characterized using FTIR, NMR, GPC, DSC, and polarized optical microscopy. The polyols showed a profound odd-even effect on the melting (T$_{m}$) and glass transition temperatures (T$_{g}$). Polyols with odd numbers of methylene groups in the alkylene units have higher transition temperatures than polyols with odd number of methylene groups. The tendency is still kept in TPEs, even though the T$_{g}$ of soft segment in TPEs are slightly higher than those of corresponding neat polyols. The T$_{m}$ and T$_{g}$ of soft segments are almost constant in the range of 20 to 60 wt % contents of soft segments. On the other hand, the normalized heat of fusion of hard segment decreased with increasing the content of loft segment.ent.t.ent.

• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1207-1210
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• 2003

The effect of solvent structure on the slope in the plot of ln K vs. solute carbon number was examined. It was found that the free energy of methylene group transfer from the gas phase into a solvent was always negative and that the absolute magnitude of interaction free energy between the methylene group and the solvent was always larger than the absolute magnitude of cavity formation free energy of the methylene group in the solvent. Thus, the slope in the plot of ln K vs. solute carbon number was always positive and its value decreases with increase of solvent polarity since the cavity formation energy of the CH₂ unit increases with increase of solvent polarity while the dispersive interaction energy of the CH₂ unit is virtually invariant. We also examined the effect of sequential addition of CH₂ unit to a solvent molecule upon ln K for three homologous series of solvents: n-alkanes, n-alcohols, and n-nitriles. Characteristic trends in the plots of ln K vs. solvent carbon number were observed for individual solvent groups. A decrease of ln K with solvent carbon number was observed for n-alkanes. An abrupt increase in ln K followed by levelling off was observed for n-alcohols while a final slight decrease in ln K after an abrupt increase followed by rapid levelling off was noted for n-nitriles. All of theses phenomena were found related to variation in cavity formation energy. It was clearly shown that a structural change of a polar solvent by sequential addition of CH₂ units causes an abrupt polarity decrease initially, then gradual levelling off, and finally, conversion to a virtually nonpolar solvent if enough CH₂ units are added.

• Journal of the Korean Graphic Arts Communication Society
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• v.13 no.1
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• pp.1-12
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• 1995

Polymeric mesogens having a regularly alternating rigid-flexible repeating structure in the main-chain polymer exhibit distinct even-odd oscillation in their thermodynamic quantities with respect to the number of methylene units in the spacer. The even-odd oscillation depends on the number of methylene groups in the spacer the entropy change at the NI(nematic-isotropic) phase transition becomes less distinct when the linking group is replaced by the carbonate. In our previous work, we have suggested that the characteristics arise from the geometrical arrangement of the linkage. In this work, we have prepared a series of carbonate-type monomer and dimer liquid crystals. The thermodynamic behaviors at the NI phase transition have been compared with those previous reported for the ether- or ester-type liquid crystals. For the dimer series, the orientational order parameter of the mesogenic core was determined by using H-NMR technique. The origin of the difference observed among linking groups was found to the geometrical characteristics of chemical structure.

• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.504-511
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• 2008

Two kinds of nitroazobenzene derivatives: 4-{4'-(nitrophenylazo)phenoxy}alkanoic acids (NAAn, n = 2~8, 10, number of methylene units in the alkyl chain) and 4-{4'-(nitrophenylazo)phenoxy}alkanoyl chlorides (NACn, n = 2~8, 10) were synthesized, and their thermotropic liquid crystalline behaviors were investigated. NAA6 formed an enantiotropic nematic phase, while the remainders, except NAA2, showed monotropic nematic phases. Isotropic-nematic transition temperature ($T_{iN}$) and change of entropy (${\Delta}S$) at $T_{iN}$ for both of NAAn and NACn varied by the change of n, and pronounced odd-even effects of n were also observed. However, the $T_{iN}$ and ${\Delta}S$ values of NAAn were much higher than those of NACn. This fact may be attributed to the hydrogen bonding between carboxyl groups. Thermal properties and degree of order in the mesophase and the magnitude of the odd-even effects of both NAAn and NACn were significantly different from those reported for 4-(alkoxy)-4'-nitroazobenzenes. It was discussed in terms of the differences in the molecular anisotropy and the temperature-dependent flexibility of the substituted groups.

• Journal of the Korean Chemical Society
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• v.26 no.3
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• pp.188-193
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• 1982

Four new thermotropic copolyesters were prepared and their liquid crystal properties were investigated by differential scanning calorimetry and on a hot-stage of a polarizing microscope. Three copolyesters had same mesogenic unit, triad aromatic ester structure, interconnected through a random combination of either odd-even, or odd-odd, or even-even number of methylene groups in the polymethylene flexible spacers. Another random copolyester consisted of mesogenic units of 1 : 1 mixture of central methyl-and bromohydroquinone moieties with two flanking p-oxybenzoate units connected by decamethylene spacer. All of the polyesters formed nematic liquid crystal phase upon melting. The transitions for melting and nematic ${\to}$ isotropic transformations could be reversibly observed by DSC as well as by microscopic study. The thermodynamic properties for their liquid crystal ${\to}$ isotropic phase transitions were discussed in relation to their chemical structures.

• Journal of Photoscience
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• v.11 no.32
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• pp.55-59
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• 2004

The present investigation is an attempt to create an optimized protocol for a bactericidal modality of different powers of He-Ne laser radiation to eliminate periodontitis disease causing bacteria from dental plaques. Periodontitis is most prevalent infectious disease of men and caused by a limited number of Gram negative oral bacteria. Porphyromonas gingivalis and Streptococcus sanguis are the important bacteria responsible for periodontitis diseases. Effect on periodontitis disease causing bacteria were produced by the exposure of different powers of He-Ne laser light i.e. 9 mW, 17 mW and 26 mW of red colour of wavelength 632.8 nm in two different periods of time i.e. 10 min. and 20 min. in the presence of dye Methylene blue (MB) used as a photosensitizer. The results have been shown in terms of percentage inhibition of colony forming units (cfu.) of bacteria. This study has shown that maximum inhibition of cfu. were observed in Laser+MB-20 min. exposure time. This inhibition was followed by Laser+MB-10 min., but minimum inhibition was seen in Laser only at 10 min. exposure. In case of effect of methylene alone on the cfu. of bacteria, it was seen that MB have not shown more inhibition of cfu. and it had shown that the no. of cfu. are very similar to that of control. The above observation of the present study was seen in case of every 3 different type of used powers of laser for both the bacteria. Maximum percentage inhibition of cfu. were seen in case of 26mW powers of He-Ne laser, which was 67. 28% to 61.42% for Porphyromonas gingivalis and Streptococcus sanguis respectively. So, increasing the power of laser (safe range for dentistry is 3-30 mW) under conditions shows an increased percentage inhibition of cfu. Thus the present investigation may be a useful adjunct with mechanical debridement in the prevention of recolonization of subgingival lesions by pathogenic microorganisms which are harmful and drug resistant.

• 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.

• Polymer(Korea)
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• v.33 no.2
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• pp.144-152
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• 2009

The thermal and optical properties of poly {1-(cholesteryloxycarbonylalkanoyloxy) ethylene}s (PCALEn, n=2$\sim$8,10, the number of methylene units in the spacer) were investigated. All of the homologues formed monotropic cholesteric phases with left-handed helical structures. PCALEn with n=2 or 10, in constrast with PCALEn 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 connecting the cholesteryl group to the polyethylene chain. The glass transition temperatures decreased with increasing n. The isotropic-cholesteric phase transition temperatures decreased with increasing n up to 7 and showed an odd-even effect. However it became almost constant when n is more than 7. This behavior is rationalized in terms of the change in the average shape of the side chain on varing the parity of the spacer. This rationalization also accounts for the observed variation of the entropy gain for the clearing transition. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for PCALEn were significantly different from those reported for cellulose tri(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the chemical structure and flexibility of main chain and the number of the mesogenic units per repeating unit.

• Polymer(Korea)
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• v.32 no.3
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• pp.230-238
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• 2008

The thermal and optical properties of cellobiose octa(cholestryloxycarbonyl)alkanoates CCCBn, $n=2{\sim}8$,10, the number of methylene units in the spacer) were investigated. All the samples formed monotropic cholesteric phases with left-handed helical structures. CCBn with n=2 or 10, in contrast with CCBn 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 connecting the cholesteryl group to the cellobiose chain. The isotropic-cholestropic transition ($T_{ic}$) and glass transition temperatures decreased with increasing n and showed no odd-even effect. The transition entropy at $T_{ic}$ increased with increasing n from 2 up 6, but at n=7 it drops significantly and then increased again with increasing n from 8 to 10. The sharp change at n=7 may be attributed to a difference in arrangement of the side groups. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for CCBn were significantly different from those reported for the cellulose tri(cholesteryloxycarbonyl)alkanoates and glucose penta(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the degree of polymerization, the number of the mesogenic units per mole-glucose unit, and the conformation of the molecules.

• 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.