• Bulletin of the Korean Chemical Society
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• v.19 no.11
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• pp.1179-1184
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• 1998

Mesogenic and azo monomers were synthesized and copolymerized to obtain two copolymers composed of methacrylate and itaconate backbone. Glass transition temperatures of the copolymers were found to be slightly higher than ambient temperature. Both the copolymers showed liquid crystalline properties. Trans-cis isomerization in film state was observed under UV-irradiation with a light of 365 nm. Regarding the photochemical phase transition behavior, the transition rate of nematic-to-isotropic state was slightly faster in the methacrylate copolymer during irradiation at 365 nm and the rate of the reverse transition was much faster in itaconate copolymer under thermal effect.

• Macromolecular Research
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• v.14 no.1
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• pp.107-113
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• 2006

Processible norbornene copolymers were realized by judiciously designing norbomene comonomers, which were themselves prepared by the Diels-Alder reaction of cyclopentadiene and benzoquinone followed by the isomerization and alkylation of alcohols. The norbornene copolymers containing these derivatized comonomers, prepared by [Pd($x_{2}CH-{3} $)$_{4}$][$SbF_{6}$]$_{2}$ catalyst, exhibited excellent solubility in many organic solvents as well as good thermal stability, as evidenced by their high glass transition ($T_{g}$) and decomposition ($\∼$350$^{circ}C$) temperatures. In addition, fairly strong adhesion to substrates such as glasses and silicon wafers was also achieved with these copolymers to overcome the limitations experienced by polynorbornene homopolymers and to make them attractive for many important industrial applications.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3641-3643
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• 2011

Multiconfigurational wavefunctions were adopted to study structural isomers, their isomerization reactions and excited states of $HN_3$. In addition to the known linear isomer, two new structural isomers were found. The three isomers can be classified as sp, $sp^2$ and $sp^3$ hybridized species, respectively. The sp3 hybridized species turned out to be the second most stable. Large reaction barriers among these species prevent thermal isomerizations. A low-lying $^3A'$ exists with a relative energy of 13.5 kcal/mol. Dramatic re-hybridization and bond elongation was found in the first excited $^1A"$.

• Bulletin of the Korean Chemical Society
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• v.28 no.6
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• pp.983-989
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• 2007

Azobenzene-cored dendrons having the photoisomerizable azobenzene core and terminal vinyl groups have been prepared. Absorption bands of azobenzene-cored dendrons are similar except more intense 280 nm band in higher generation azobenzene dendron. All three azobenzene-cored dendrons show reversible photoisomerization similar to simple azobenzene, irrespective of the generation of dendron. On 350 nm irradiation, absorption band around 344 nm decreases and 436 nm band increases. Photoisomerization reactions are very fast for all three azobenzene-cored dendron and the reaction efficiency is dependent of its generation and solvent. In the dark, slow thermal reversion to original absorption spectrum is observed.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.763-767
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• 2019

In this study, thermal decomposition characteristics of exo-tetrahydrodicyclopentadiene (exo-THDCP) composed with a single compound were analyzed by using a flow reactor. The experiments were carried out at $500^{\circ}C$, 50 bar and the products of each flow rate condition were analyzed by using a GC/MS. As a result, it was confirmed that exo-THDCP was decomposed mainly into cyclic compounds and a part was isomerized by heat. As the flow rate was increased, the kinds and ratio of compounds produced through the decomposition and isomerization were decreased. Also, the conversion rate of exo-THDCP and the amount of heat absorbed during the decomposition were also decreased. The compounds rapidly produced by decomposition were mainly formed through the radical form of 1-cyclopentylcyclopentene (1-CPCP) which is one of the intermediates that can be formed from exo-THDCP because it has the lowest activation energy of 42 kcal/mol.

• Journal of the Korean Applied Science and Technology
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• v.31 no.1
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• pp.50-58
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• 2014

A novel fullerene derivative with photoresponsive azobenzene group was designed and synthesized, and its photoresponsive properties were reported. Starting from 4-nitrophenol, compound 1, which is containing fullerene moiety connected to azobenzene group through covalent linkage was synthesized by 5 steps. All the intermediates and the final compound were characterized by $^1H$, $^{13}C$-NMR, FAB-Mass or elemental analysis. Compound 1 exhibited the expected photoresponsive behavior. Chloroform solution($10^{-5}M$) of it served to maximize the absorption at 351 nm corresponding to the trans-azobenzene chromophore. Irradiation of this solution with 365 nm light resulted in photoisomerization to cis-azobenzene, as evidenced by decrease in the absorbance at 351 nm and an increase in absorbance at 450nm. A photostationary state was reached within about 150 s. Thermal reversion to the original spectrum was observed over the course of about 6 h at room temperature in the dark. However, exposure to bright sun light for about 5 s also effect almost complete reversion to the trans-isomer. This indicates that there is no strong steric influence on the trans-cis reversible isomerization of compound 1.

• Polymer(Korea)
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• v.38 no.6
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• pp.774-781
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• 2014

Acetylenic or phenylethynyl end-capped polyisoimide oligomers ($M_w$ 2500 g/mol, 5000 g/mol) based upon 4,4'-diamino diphenyl ether (4,4'-ODA)/4,4'-oxydiphthalic anhydride (ODPA) and 4,4'-ODA/3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) were synthesized by using 4-ethynylaniline (4-EA) or 4-phenylethynyl phthalic anhydride (4-PEPA) as an end capper. The incorporation of ethynyl groups were confirmed by FTIR spectroscopy. The isomerization temperature was influenced by molecular weight as well as the backbone structure of polyisoimides oligomers. Thus, polyisoimide oligomers with molecular weight of 2500 g/mol was found to be imidized at temperature $10^{\circ}C$ lower than that for the oligomers with molecular weight of 5000 g/mol. The crosslinking reaction of ethynyl groups occurred at a higher temperature than that for the isoimide/imide isomerization reaction. These two reactions were totally or partially overlapped on the DSC thermograms for the polyisoimide oligomer end-capped with 4-EA. Kinetics of thermal imidization and crosslinking reactions for the 4,4'-ODA/ODPA polyisoimide oligomers end-capped with 4-PEPA were investigated by performing dynamic DSC experiments at heating rate of $10^{\circ}C/min$. The activation energy and pre-exponential factors were 141 kJ/mol and $1.45{\times}10^{13}min^{-1}$ for the imidization reaction and 177 kJ/mol and $2.90{\times}10^{13}min^{-1}$ for the crosslinking reaction, respectively.

• 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.