• Journal of the Korea Academia-Industrial cooperation Society
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• v.11 no.4
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• pp.1367-1372
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• 2010

Copoly(ether-ether-ester)s having flexible side chain were synthesized by polycondensation. Intrinsic viscosities of polymers were between 0.42 and 0.78dl/g in tetrachloroethane. The polymer structures were investigated by $^1H$-NMR and FT-IR, and thermal and liquid crystalline properties of polymers were measured by DSC, TGA, POM and XRD. As results of investigations, synthetic copolymers exhibited lower melting temperature than homopolymers. When the biphenylene units contents in copolymer were more than 60 mol %, nematic mesophase was observed, and the mesophase of synthetic polymers was dependent upon biphenylene content.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.10 no.11
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• pp.3060-3065
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• 2009

A series of wholly aromatic Poly(ether-ether-ester)s with flexible side chain was synthesized by direct polycondensation from ether linkaged triad diol and 2,5-dialkoxyterephthalic acid. The chemical structures and physical properties of these polymers were investigated by using $^1H$-NMR, FT-IR, DSC and TGA. As results of investigations, the inherent viscosities($\eta$inh) measured at $40^{\circ}C$ in 1,1,2,2-tetrachloroethane(TCE) were 0.45~0.86 dl/g and initial decomposition(Td) in TGA occurred at 378~418 $^{\circ}C$ in N2 gas. The majority of these polymers were soluble in organic solvents used in this experiments at elevated temperatures. Melting temperatures(Tm) decreased with increasing the length of the side chain and showed odd-even effects.

• Textile Coloration and Finishing
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• v.15 no.4
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• pp.24-31
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• 2003

In this research, we applied FT-IR spectroscopy to study the hydrolysis of the ester-crosslinking formed by various polycarboxylic acids on the cotton fabric. We observed the following; (1) the ester-crosslinking is less durable to hydrolysis than ether-crosslinking under all conditions; (2) the ester-crosslinking formed by polycarboxylic acids having more than three carboxyl groups, such as butanetetracarboxylic acid (BTCA), are substantially more durable to hydrolysis than the acids having two or three carboxyl groups, such as maleic and citric acid; (3) alkaline conditions drastically accelerate the hydrolysis of both urea- and ester-crosslinking; and (4) the ester-crosslinking formed by poly(maleic acid) is more resistant to hydrolysis at alkaline conditions than BTCA. (5) polycarboxylic acid molecules were removed from the fabric at same rate as the hydrolysis of the ester linkage. FT-IR spectroscopy has proved to be a useful analytical technique for evaluating the hydrolysis of the crosslinked cotton fabric.

• Applied Biological Chemistry
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• v.17 no.3
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• pp.149-176
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• 1974

Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

• Applied Chemistry for Engineering
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• v.26 no.4
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• pp.445-451
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• 2015

Semi-flexible liquid crystalline polymers containing a mesogenic group and an octamethylene flexible spacer in the main chain were synthesized by solution polycondensation. The mesogenic group in the polymer consists of four aromatic rings connected by ester and ketone, ether, sulfide, methylene, sulfone, or isopropylidene linkage groups. This paper discusses effects of the central linker of the mesogenic group on polymer properties. The structures and properties of synthesized polymers were investigated by $^1H$-NMR, FT-IR, differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), X-ray diffractometer (XRD), and polarizing optical microscope (POM). Polymers having bent linkage groups exhibited low thermal transition temperatures, narrow mesophase temperature ranges, low liquid crystallinity, and good solubilities in organic solvents, while those having bulky linkage groups were amorphous and exhibited high glass transition temperatures.

• 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.

• Bulletin of the Korean Chemical Society
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• v.29 no.6
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• pp.1167-1172
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• 2008

We investigated the glass transition temperatures ($T_g$) of dendrons consisting of conformationally mobile aliphatic polyether dendritic cores plus glassy peripheral polystyrenes (PSs), and linear PSs in the molecular weight range of 1000-8500 g/mol. We compared their $T_g$ behavior depending on their polymeric architecture. The linear PSs show a typical growth of $T_g$ up to 92.5 ${^{\circ}C}$ as the molecular weight increases to 8300 g/mol, while the dendrons display nearly constant $T_g$ values of 58-61 ${^{\circ}C}$, despite the increase of molecular weight with each generation. The striking contrast of Tg behavior would be mainly attributed to the fact that the dendrons keep the ratio of $N_e$/M ($N_e$: number of peripheral chain ends, M: molecular weight) over all the generations. Additionally, for the influence of dendritic spacers on glass transition temperature we prepared dimeric PSs with different linkage groups such as aliphatic ether, ester and amide bonds. We found that the dimer with the ether spacer exhibited the lowest glass transition at 55.4 ${^{\circ}C}$, while the amide linked dimer showed the highest glass transition temperature at 74.2 ${^{\circ}C}$. This indicates that the peripheral PS chains are effectively decoupled by the conformationally flexible ether spacer. The results from this study demonstrated that polymeric architecture and dendritic core structures play a crucial role in the determination of glass transition behavior, providing a strategy for the systematic engineering of polymer chain mobility.

• Applied Chemistry for Engineering
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• v.21 no.2
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• pp.230-237
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• 2010

A homologous series of linear liquid crystal dimers, ${\alpha},{\omega}$-bis(4-nitroazobenzene-4'-carbonyloxy)alkanes (NATWESn, n = 2~8, 10, the number of methylene units in the spacer) have been synthesized, and the thermal behavior of the series has been investigated. All the dimers formed 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 behavior was rationalized in terms of the change in the average shape of the spacer on varing 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 NATWESn were very similar to those of the corresponding ether compounds, while they were significantly different from those of the monomesogenic compounds, 4-{4'-(nitrophenylazo)phenoxy}alkanoyl chlorides and the side-chain liquid-crystalline polymers, the poly[1-{4-(4'-nitrophenylazo) phenoxycarbonylalkanoyloxy}ethylene]s. The results were discussed in terms of the 'irtual 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.