• Applied Chemistry for Engineering
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• v.10 no.6
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• pp.828-831
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• 1999

5,15-Bis(mesityl)-10,20-bis(4-amino)porphyrin was synthesized with meso-(mesityl)dipyrromethane and 4-nitrobenzaldehyde. It was characterized with $^1H$-NMR spectroscopy, UV spectrophotometer, and GC-MASS. In UV spectrum, Soret-band(438 nm) and Q-bands(526, 572, 611 nm) were confirmed. In NMR spectrum, the characteristic peak of porphyrin was detected at -2.65 ppm. Copolyimide containing porphyrin structure was synthesized with mesityl-$TPP(NH_2)$, 3,3',4,4'-benzophenonetetracarboxylic dianhydride(BTDA) and 2,2-bis(4-(4-aminophenoxy)phenyl) hexafluoropropane(BAPHF) and characterized with UV and FT-IR spectrophotometer. The $T_g$ and $T_m$ of the synthesized copolyimide were 220.7 and $369.2^{\circ}C$, respectively.

• Polymer(Korea)
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• v.32 no.3
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• pp.256-262
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• 2008

Copolyimides containing pendant trifluoromethyl ($CF_3$) groups were synthesized from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS) with various concentrations of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane(BAPP) to poly(amic acid)(PAA), followed by thermal imidization. These copolyimides were readily soluble in N,N'-dimethylacetamide (DMAc) and could be solution-cast into a flexible and tough film. The thermomechanical properties, morphology and an optical transparency of the copolyimide films were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), scanning electron microscopy (SEM), universal tensile machine (UTM), and a UV-Vis spectrometer. The cast copolyimide films exhibited high optical transparency with a cut-off wavelength (${\lambda}_0$) of $275{\sim}319\;nm$ in UV-vis absorption and a low yellow index(YI) value of $3.65{\sim}10.37$. The thermo-mechanical properties of copolyimide films were enhanced linearly with increasing a BAPP content. In contrast, the optical transparency of the copolyimide films was found to get worse with increasing a BAPP content.

• Proceedings of the Membrane Society of Korea Conference
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• 2004.11a
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• pp.88-92
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• 2004

• Polymer(Korea)
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• v.32 no.6
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• pp.580-586
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• 2008

Copolyimides were synthesized from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 1,3-bis(3-aminophenoxy)benzene (BAPB) with different mole ratios of 2,2-bis[4-(4-aminophenoxy)pheny1]hexafluoropropane (BAPP). The solution cast film of poly(amic acid) (PAA) was heat treated at different temperatures to create copolyimide films. The PI copolymer films were found to exhibit good optical transparencies. The thermomechanical properties, morphology, and optical transparency of PI films were examined using fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (XRD), scanning electron microscopes (SEM), differential scanning calorimeter(DSC), thermo-gravimetric analyzer (TGA), universal tensile machine (UTM), and IN - Vis. spectrometer. The glass transition temperature ($T_g$), ultimate strength, and initial modulus linearly increased with increasing BAPP mole fraction. However, thermal stability($T_D{^i}$) of the copolyimide remains constant regardless of BAPP loadings. It was found, however, that the optical transparency decreases slightly upon increasing the BAPP content because of the formation of the charge transfer complexes.

• 한국정보디스플레이학회:학술대회논문집
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• 2000.01a
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• pp.191-192
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• 2000

New copolyimides containing nitrile side group were synthesized from copolymerization of pyromellitic dianhydride, m-phenylene diamine and 3,5-diaminobenzonitrile and subsequent thermal imidization of the resulting poly(amic acid). Crystallinity, glass transition temperature and initial decomposition temperature of copolyimides were almost identical to those of homo polyimide prepared from PMDA and m-PDA. Change of pretilt angle induced by the orientation layer of resulting copolyimide was investigated by using a nitrile-containg nematic liquid crystal cell after rubbing. As the content of polar nitrile group was increased in the copolymer, pretilt angle was increased from $3.65^{\circ}$ to $6.49^{\circ}$. The mechanism of this was speculated as the dipolar interaction between the liquid crystal and nitrile groups in copolyimide.

• Membrane Journal
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• v.17 no.4
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• pp.287-293
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• 2007

Pervaporation separation of toluene from water were studied using hydrophobic copolyimide membranes. The copolyimide membranes were prepared from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and two diamines (polysiloxane diamine (SIDA)/2-(perfluorohexyl) ethyl-3,5-diaminobenzene (PFDAB)). The pervaporation properties for toluene/water were investigated in terms of mol ratio of SIDA/PFDAB in polyimide membranes. Sorption- and diffusion-related properties were measured to analyze the permeation properties in solution-diffusion theory, It was found that as the SIDA content in the membranes increased, sorption of toluene and sorption selectivity of toluene/water increased due to high affinity of siloxane moiety toward toluene. Diffusion coefficient of toluene and diffusion selectivity of toluene/water also increased with SIDA content due to high free volume of siloxane moiety. As the results, the permeation flux and pervaporation selectivity increased markedly from 0.005 $kg/m^2h$ to 049 $kg/m^2h$ and from 9 to 6380, respectively.

• Polymer(Korea)
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• v.39 no.2
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• pp.275-280
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• 2015

Two series of copolyimides (Co-PIs) were prepared by reacting 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 1,2,4,5-benzentetra carboxylic dianhydride (pyromellitic dianhydride) (PMDA), as dianhydrides based on 4,4'-biphthalic anhydride (BPA) and 2,2'-bis(trifluoromethyl)benzidine (TFB) by using thermal- and chemical imidizations. Co-PIs films with different dianhydride monomer compositions were compared in terms of their thermal properties and optical transparencies. The addition of PMDA was more effective than the addition of 6FDA for improving the thermal properties. Meanwhile, 6FDA is more effective in optical transparencies.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1014-1019
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• 1999

Copolyamic acid PMDA/6FDA-PDA(PAA) and homopolyamic acids PMDA-PDA(PAA) and 6FDA-PDA(PAA) were synthesized from 1,2,4,5-benzenetetracarboxylic dianhydride(PMDA) and 2,2'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride(6FDA) as the dianhydride and 1,4-phenylenediamine (PDA) as the diamine. Residual stresses were detected in-situ during thermal imidization of the co- and homopolyimide precursors as a function of processing temperature over the range of $25{\sim}400^{\circ}C$ using thin film stress analyzer(TFSA), and morphological structures were investigated by WAXD. In comparison, the resultant residual stress of polyimide films composed of different compositions decreased with the increasing content of PMDA unit in the chain and was about 5 Mpa in compression mode for PMDA-PDA. In this study, the synthesis of random PMDA/6FDA-PDA copolyimide could be completed and compensate for the difficulty of process due to high $T_g$ of PMDA-PDA and relatively higher stress of 6FDA-PDA. It showed that we can make a low level stress copolyimied having excellent mechanical properties by incorporating appropriate rod-like rigid structure PMDA-PDA unit into 6FDA-PDA polyimide backbone which generally shows higher stress due to rotational hinges such as bulky di(trifluoromethyl). Specially, PMDA/6FDA-PDA(0.9:0.1:1.0) satisfied excellent mechanical property and low level stress as an inter layer showing low dielectric constant.

• Membrane Journal
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• v.16 no.4
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• pp.241-251
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• 2006

In this study, crosslinked copolyimides with random (r-) and block (b-) structure were fabricated using N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and pentanediol as crosslinkers. Linear r- and b-sulfonated copolyimides were also fabricated for comparison. Ion exchange capacities of r- and b-copolyimides were very similar to each other owing to their strong dependence of sulfonic acid content. The physical crosslinking via dimerization of carboxylic acid groups induced a reduced average interchain distance in b-copolyimide without crosslinkers. Consequently, its water uptake and methanol permeability were lower than those of r-sulfonated copolyimides. Simultaneously, the reduced interchain distance increased the content of fixed-charged ions per unit volume. The high fixed-charged ion density contributed to an enhancement of proton conductivity In the b-sulfonated copolyimide. Crosslinking caused the reduction of average interchain distance between polymer chains irrespective of types of crosslinker and polymer structure, leading to low methanol permeability. On the contrary, their proton conductivity was improved owing to formation of effective hydrophilic channels responsible for proton conduction. In particular, this trend was observed in r-copolyimide containing a fixed charged ion.

• Polymer(Korea)
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• v.38 no.5
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• pp.632-639
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• 2014

2,7-Dihydroxynaphthalene bis(trimellitate anhydride) (2,7-TA) was synthesized from trimellitic anhydride chloride and 2,7-dihydroxynaphthalene. Copolyimides (Co-PI) containing ester group were synthesized from 2,7-TA, pxylylenediamine, and 2,2'-bis(trifluoromethyl)benzidine (TFB). The Co-PI films were obtained from poly(amic acid) by solution casting through thermal imidization on a glass plate. The thermal property, gas permeation, and optical transparency of the Co-PI films with various TFB monomer contents were investigated. These Co-PIs could be solution-cast into a flexible and tough film. The cast Co-PI films exhibited high optical transparency with a cut-off wavelength of 370~395 nm in UV-vis. absorption and a low yellow index value of 3.55~7.63. The thermal property of Co-PI films increased linearly with increasing TFB content. However, the oxygen permeation and optical transparency of the Co-PI films was found to worsen with increasing TFB content.