• 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.

• Macromolecular Research
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• v.17 no.11
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• pp.912-918
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• 2009

An optically active diacid containing the L-histidine moiety was prepared by reacting pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic acid 1,2,4,5-dianhydride) 1 with L-histidine 2 in acetic acid, and was polymerized with several aromatic diamines 5a-g to obtain a new series of optically active poly(amide-imide)s (PAIs) using two different methods, such as direct polycondensation in a medium consisting of N-methyl-2-pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride ($CaCl_2$)/pyridine (Py) and direct polycondensation in a tosyl chloride (TsCl)/pyridine (Py)/N,N-dimethylformamide (DMF) system as a condensation agent. The resulting new polymers 6a-g with inherent viscosity was obtained in good yield. The polymers were readily soluble in polar organic solvents, such as N,N-dimethyacetamide (DMAc), N,N-dimethyformamide (DMF), and dimethyl sulfoxide (DMSO). The obtained polymers were characterized by FTIR, specific rotation, elemental analysis as well as $^1$H-NMR spectroscopy and gel permeation chromatography (GPC). The thermal stability of the resulting PAIs was evaluated with thermogravimetric analysis techniques under a nitrogen atmosphere.

• Applied Chemistry for Engineering
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• v.28 no.2
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• pp.237-244
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• 2017

Hyperbranched liquid crystalline polymers with azomesogenic and cholesteryl groups in their terminal positions were designed and synthesized by direct polycondensation reaction. The chemical structures and thermal and mesomorphic properties of the synthesized polymers were investigated by FT-IR, $^1H-NMR$, differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and polarizing optical microscopy (POM). The inherent viscosities (${\eta}_{inh}$) of the polymers were measured to be between 0.30 and 0.50 dL/g in phenol/p-chlorophenol/1,1,2,2-tetrachloroethane (25/40/35 = w/w/w). The degree of branching (DB) in these polymers ranged from 0.37 to 0.75; they, as amorphous polymer, showed glass transition temperatures ranging from 80 to $120^{\circ}C$; the polymers readily dissolved in most of the organic solvents used in the experiments. Only hyperbranched polymers with a cholesteryl group as their mesogenic group showed liquid crystalline phases.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.11 no.10
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• pp.4041-4046
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• 2010

Wholly aromatic polyesters having flexible alkoxy side chain were synthesized by direct polycondensation. The synthetic polymers have been characterized by $^1H$-NMR, FT-IR. DSC, TGA, optical polarizing microscope and X-ray diffractometer. The inherent viscosities (${\eta}_{inh}$) measured in 1,1,2,2-tetrachloroethane (TCE) were 0.46~2.41 dL/g. The polymers having side chain showed double melting transition, ie, solid-sanidic liquid crystalline (LC) phase transition ($T_{m1}$) and sanidic LC phase-nematic LC phase transition ($T_{m2}$). As incresing length of alkoxy side chain, phase transition temperatures decreased and solubilities in organic solvents incresed. The peaks of $2{\theta}\;{\simeq}5$ and $2{\theta}\;{\simeq}20$ in X-ray diffractograms are due to crystallization of polymer main chain and of long side chain, respectively.

• Elastomers and Composites
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• v.51 no.3
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• pp.195-205
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• 2016

A series of aromatic poly(hydroxyamide)s (PHAs) containing varying oligo(oxyethylene) substituents and 1,3-phenylene imide ring unit in the main chain were synthesized by the direct polycondensation reaction. The inherent viscosities of the PHAs exhibited in the range of 0.89~1.12 dL/g in DMAc or DMAc/LiCl solution. The PH-2~5 copolymers were easily soluble in strong aprotic solvents: DMAc, NMP, DMSO etc. and the PH-5 copolymer was soluble in less polar solvents such as m-creasol and pyridine with LiCl salt on heating. However, all PBOs were quite insoluble in other solvents, but only partially soluble in sulfuric acid. All copolymers (PH-2~5) could afford the flexible and tough films by solution casting. We identified that the PHAs were converted to the PBOs by the thermal cyclization reaction in the range of $200{\sim}380^{\circ}C$. The 10% weight loss temperatures and char yields of the PBOs were recorded in the range of $382{\sim}647^{\circ}C$ and 38.7~73.1% values at $900^{\circ}C$. The tensile strength and initial modulus of the PH-5 in the copolmers showed the highest values of 2.46 GPa and 49.55 MPa, respectively. The LOI values of the PHAs were in the range 26.6~29.0%, and increased with increasing 1,3-phenylene imide ring unit.

• 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.

• 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.

• Elastomers and Composites
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• v.55 no.3
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• pp.205-214
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• 2020

A series of wholly aromatic polyhyroxyamide (PHA) copolymers were prepared by direct polycondensation reaction of isophthalic acid and diacids containing bulky units with 3,3'-dihydroxybenzidine. The inherent viscosities of the PHAs measured at 35℃ in DMAc solution were in the range of 0.31-0.56 dL/g. The solubility study revealed that the PHAs were readily soluble in aprotic solvents such as, dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) at room temperature and in less polar solvent such as pyridine. However, the polybenzoxazole (PBO) copoymers were quite insoluble in all organic solvents except partially soluble in concentrated sulfuric acid and partially soluble in NMP containing LiCl. The PBO copolymers showed maximum weight loss temperature in the range of 593-632℃ and high char yields in the range of 65.0-71.2% at 900℃ in a nitrogen atmosphere.

• Elastomers and Composites
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• v.46 no.4
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• pp.295-303
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• 2011

A series of new aromatic polyhydroxyamides (PHAs) containing imide ring were prepared by direct polycondensation reaction of imide-diacids and two types of bis(o-aminophenol)s including 3,3'-dihydroxybenzidine and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The polymers were characterized by FT-IR, FT-NMR, DSC and TGA. The inherent viscosities of the PHAs measured at $35^{\circ}C$ in DMAC solution were in the range of 0.49-1.13 dL/g. PHA 2 and 3, except PHA 1, were soluble in polar solvents such as DMAc, DMF and NMP. PHA 4, 5, and 6 containing 6F group showed a higher solubility in less polar solvents. But the polybenzoxazoles (PBOs,) were insoluble in a variety of solvents except partially soluble in sulfuric acid. The PBO 1, 2 and 3 showed maximum weight loss temperature in the range of $650-656^{\circ}C$ and relatively high char yields in the range of 57.4-61.9 % under a nitrogen atmosphere. These results suggested that the introduction of imide or diimide ring in the main chain was effective in improving the thermal stability of PHAs and PBOs.