• Macromolecular Research
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• v.10 no.5
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• pp.241-245
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• 2002

A new aromatic diamine monomer containing benzoxazole substituents was prepared by a multi-step synthesis starting from 1,4-dibromo-2,5-difluorobenzene. This bulky and disc-shaped monomer was polymerized with commercial dianhydride monomers to give several different poly(amic acid)s with their inherent viscosities in the range of 0.24-0.35 dL/g. The prepared polymers were soluble in typical polar aprotic solvents. Thermal imidization to the corresponding polyimides were investigated by using FT-IR, DSC and TGA.

• Macromolecular Research
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• v.14 no.4
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• pp.438-442
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• 2006

Novel sulfonated poly(aryl ether ketones) containing benzoxazole were directly synthesized by aromatic nucleophilic polycondensation using various ratios of 2,2'-bi[2-( 4-flurophenyl)benzoxazol-6-yl]hexafluoropropane to sodium 5,5'-carbonylbis(2-fluorobenzenesulfonate). The copolymers were soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide at a relatively high solid composition (>15 wt%) and formed tough, flexible and transparent membranes. The membranes exhibited a degradation temperature of above $290^{\circ}C$. The exact dissolution times of these membranes at $80^{\circ}C$ in Fenton's reagent (3 wt% $H_2O_2$ containing 2 ppm $FeSO_4$) were undetectable, confirming their excellent chemical stability in fuel cell application. The membranes showed a moderate increase in water uptake with respect to increasing temperature. The proton conductivities of the membranes were dependent on the composition and ranged from $1.10{\times}10^{-2}$ to $5.50{\times}10^{-2}Scm^{-1}$ at $80^{\circ}C$ and 95% relative humidity (RH). At $120^{\circ}C$ without externally humidified conditions, the conductivities increased above $10^{-2}Scm^{-1}$ with respect to increasing benzoxazole content, which suggested that the benzoxazole moieties contributed to the proton conduction.

• Elastomers and Composites
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• v.54 no.4
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• pp.321-329
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• 2019

A series of poly(hyroxyamide)s (PHAs) was prepared by direct polycondensation reaction of 4,4'-(2,3-pyridinedioxy)dibenzoic acid and/or isophthalic acid with 3,3'-dihydroxybenzidine. The yield percentages of the products were high, and the inherent viscosities of the polymer in DMAc solution at 35℃ were 0.31-0.59 dL/g. All PHA polymers were found to be soluble in polar aprotic solvents such as DMAc, DMSO, NMP, and DMF. On the other hand, LiCl was required to dissolve IPHA-1 in aprotic solvents. Poly(benzoxazole)s (PBOs) were partially soluble in conc-H₂SO₄; IPBO-4, -5, and -6 were partially soluble in NMP only when LiCl was added to the solution, and the solution was heated. The PBO polymers showed a maximum weight loss in the temperature range of 654-680℃, and the char yields at 900℃ under nitrogen atmosphere exceeded 63%.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.896-900
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• 2000

A study was done on the synthesis of new poly(arylene ether)s and poly(arylenesulfide) with rigid benzoxazole pendants using nucleophilic aromatic substitution reaction. As a new aromatic monomer, 1,4-bis(2-benzox-azolyl)-2,5-difluorobenzene [I] w as synthesized in three steps starting from 1,4-dibromo-2,5-difluorobenzene. A model reaction of difluoro monomer [I] with two equivalents of m-cresol or thiophenol in a typical ether con-densation reaction conditions gave very high yields ( > 93%) of the desired disubstituted product, suggesting the feasibility of polymer formation in these reaction system. Monomer[I] was polymerized with bisphenols and bisbenzenethiol in NMP using K2CO3 as base. The molecular weight of the resulting polymers, however,seemed relatively low according to their solution viscosity values ( ηinh = 0.15-0.29 dL/g). The poly(arylene ether)s were soluble in several common organic solvents including chloroform, pyridine and N,N'-dimethylfor-mamide. The poly(arylene sulfide) was, however, ony soluble in strong acids like sulfuric acid and trifluoro-acetic acid. The glass transition temperatures were found to be 175-215 $^{\circ}C.$ These polymers were stable up to 380-420 $^{\circ}C$ in both nitrogen and air, as determined by the temperature that a significant weight loss began to appear on TGA.

• Elastomers and Composites
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• v.50 no.2
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• pp.138-145
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• 2015

A series of wholly aromatic poly(hydroxyamide)s(PHAs), containing varying amounts of 2,6-dimethylphenoxy group and quinoxaline ring in the main chain, were synthesized by a direct polycondensation method. The inherent viscosities of the PHAs in either DMAc or DMAc/LiCl solution at $35^{\circ}C$ were found to be in the range of 1.02~1.90 dL/g. In the solubility study, we observed that PHA 1, PHA 2, and PHA 3 were dissolved in aprotic solvents such as DMAc, NMP, DMF, and DMSO with LiCl on heating; however, PHA 4, PHA 5, and PHA 6 could be dissolved in aprotic solvents on heating without LiCl. For poly(benzoxazole)s(PBOs), the 10% and maximum weight loss temperatures were in the range of $582{\sim}622^{\circ}C$ and $630{\sim}659^{\circ}C$, respectively. Residues of PBOs at $900^{\circ}C$ were found to be relatively high, which were in the range of 65.3~70.8%.

• Elastomers and Composites
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• v.53 no.3
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• pp.141-149
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• 2018

A series of aromatic poly(o-hydroxyamide)s (PHAs) were synthesized by the direct polycondensation reaction of 4,4′-(2,3-quinoxalinedioxy) dibenzoic acid and/or 4,4′-(2,3-pyridinedioxy) dibenzoic acid with bis(o-aminophenol) including 2,2-bis-(amino-4-hydroxyphenyl)hexafluoropropane. The PHAs exhibited inherent viscosities in the range of 0.17-0.35 dL/g at $35^{\circ}C$ in a DMAc solution. These polymers showed low inherent viscosities and yielded brittle films. All the PHAs showed excellent solubility in aprotic solvents such as DMAc, DMSO, NMP, and DMF at room temperature and in less polar solvents such as pyridine and THF. However, all the PBOs were only partially soluble in $H_2SO_4$. The PBOs exhibited 10% weight loss at temperatures in the range of $537-551^{\circ}C$. The maximum weight loss temperature increased with an increase in the content of the quinoxaline-containing monomer. The residue of the PBOs showed a weight loss of 45.8-56.7% at $900^{\circ}C$ in a nitrogen atmosphere.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3279-3284
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• 2012

Poly(benzimidazole-co-benzoxazole)s (PBI-co-PBO) are synthesized by polycondensation reaction with 3,3'-diaminobenzidine, terephthalic acid and 3,3'-dihydroxybenzidine or 4,6-diaminoresorcinol in polyphosphoric acid (PPA). All polymer membranes are prepared by the direct casting method (in-situ fabrication). The introduction of benzoxazole units (BO units) into a polymer backbone lowers the basic property and $H_3PO_4$ doping level of the copolymer membranes, resulting in the improvement of mechanical strength. The proton conductivity of $H_3PO_4$ doped PBI-co-PBO membranes decrease as a result of adding amounts of BO units. The maximum tensile strength reaches 4.1 MPa with a 10% molar ratio of BO units in the copolymer. As a result, the $H_3PO_4$ doped PBI-co-PBO membranes could be utilized as alternative proton exchange membranes in high temperature polymer electrolyte fuel cells.

• Elastomers and Composites
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• v.47 no.4
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• pp.355-363
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• 2012

A series of poly(hydroxyamide)s (PHAs) having trifluoromethyl group were prepared by direct polycondensation of aromatic diimide-dicarboxylic acids with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane by thionyl chloride and triethyl amine in N-methyl-2-pyrrolidinone (NMP). The PHAs exhibited inherent viscosity in the range of 0.54-0.96 dL/g at $35^{\circ}C$ in DMAc solution. All PHAs were readily soluble in a variety of organic solvents, whereas the polybenzoxazoles (PBOs) were quite insoluble except partially soluble in sulfuric acid. PHAs were converted to PBOs by thermal cycling reaction with heat of endotherm. The maximum weight loss temperature of the PHAs occurred in the range of $559-567^{\circ}C$. The PBOs showed relatively high char yields in the range of 47-59%. Pyrolysis Combustion Flow Calorimeter (PCFC) results of the PBOs showed 12-19 W/g heat release rate (HRR), and 2.7-3.6 kJ/g total heat release (total HR). The HRR of PBO 1 showed the lowest value of 12 W/g, which was 37% lower than that of PBO 3 (19 W/g).

• Elastomers and Composites
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• v.50 no.3
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• pp.175-183
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• 2015

A series of fluorinated aromatic poly(hydroxyamide)s (PHAs) were synthesized by direct polycondensation of diacides containing 2,6-dimethylphenoxy group and quinoxaline ring in the main chain with 2,2-bis-(3-amino-4-hydroxyphenyl) hexafluoropropane. The PHAs had relatively low inherent viscosities in the range of 0.35~0.43 dL/g at $35^{\circ}C$ in DMAc solution. All PHAs exhibited excellent solubility in aprotic solvents such as NMP, DMAc, DMF and DMSO as well as in common organic solvents such as pyridine, THF, and m-cresol at room temperature. However, the poly(benzoxazole)s (PBOs) were quite insoluble in all organic solvents except partially soluble in concentrated sulfuric acid. The PBOs showed glass transition temperatures between 233 and $284^{\circ}C$ by DSC and maximum weight loss temperatures in the range of $536-546^{\circ}C$ by TGA.

• Environmental Analysis Health and Toxicology
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• v.13 no.3_4
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• pp.55-61
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• 1998

Glutathione-S-transferases (GSTs) detoxify electrophilic xenobiotics and reactive metabolites. Recently benzene-fused heterocycles have been shown to increase the total amount of hepatic GSTs in rats. Primarily this study aimed to determine the induction of GSTs by benzoazoles (BAs) including benzoxazole (BX), 2-methylbenzoxazole (M-BX), 2,5-dimethyl benzoxazole (D-BX), benzothiazole (BT), aminobenzothiazole (A-BT) and 2-mercaptobenzothiazole (M-BT) in rats. Hepatic cytosol and poly(A)$^+$ mRNA were prepared from rats after oral administration of BX, BT, M-BX, D-BX, A-BT and M-BT for 5 consecutive days at doses of 1 mmol/kg. Western immunoblot and northern blot analysis were conducted with rabbit anti-GST Ya, Yb$_1$, Yb$_2$, Yc antibodies and cDNA probes containing = 500 bps in the specific coding regions of Ya, Yb$_1$, Yb$_2$, Yc$_1$, and Yc$_2$, respectively. All BAs increased the amount of enzymes and mRNA levels of GSTs. BT was the most effective inducer of GSTs among the compounds examined in this study. Although A-BT and M-BT, the derivatives of BT, induced GSTs, these chemicals had lesser effect on induction of GSTs than BT. The derivatives of BX also induced less GSTs than the parent compound and the addition of methyl group to the benzene ring of BX reduced the induction of GSTs. BAs had better inductive effects on the class $\alpha$(Ya, Yc) than class $\mu$ GSTs (Yb$_1$, Yb$_2$). BAs enhanced mRNA levels of GSTs in parallel with the protein levels. These results indicate that 1) most of BAs induced various isozymes of GSTs, 2) the induction of GSTs appears to be correlated with the chemical structure of the derivatives, and 3) the expression of GST by BAs is presumably under the transcriptional regulation.