• Carbon letters
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• 제12권1호
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• pp.31-38
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• 2011

This study experimentally investigated dicyclohexylammonium 2-cyanoacrylate (CA) as a potential comonomer for polyacrylonitrile (PAN) based carbon fiber precursors. The P(AN-CA) copolymers with different CA contents (0.19-0.78 mol% in the feed) were polymerized using solution polymerization with 2,2-azobis(isobutyronitrile) as an initiator. The chemical structure and composition of P(AN-CA) copolymers were determined by proton nuclear magnetic resonance and elemental analysis, and the copolymer composition was similar to the feeding ratio of the monomers. The effects of CA comonomer on the thermal properties of its copolymers were characterized differential scanning calorimetry (DSC) in nitrogen and air atmospheres. The DSC curves of P(AN-CA) under nitrogen atmosphere indicated that the initiation temperature for cyclization of nitrile groups was reduced to around $235^{\circ}C$. The heat release and the activation energy for cyclization reactions were decreased in comparison with those of PAN homopolymers. On the other hand, under air atmosphere, the P(AN-CA) with 0.78 mol% CA content showed that the initiation temperature of cyclization was significantly lowered to $160.1^{\circ}C$. The activation energy value showed 116 kJ/mol, that was smaller than that of the copolymers with 0.82 mol% of itaconic acids. The thermal stability of P(AN-CA), evidenced by thermogravimetric analyses in air atmosphere, was found higher than PAN homopolymer and similar to P(AN-IA) copolymers. Therefore, this study successfully demonstrated the great potential of P(AN-CA) copolymers as carbon fiber precursors, taking advantages of the temperature-lowering effects of CA comonomers and higher thermal stability of the CA copolymers for the stabilizing processes.

• Fibers and Polymers
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• 제6권2호
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• pp.103-107
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• 2005

An attempt was made to correlate the polymerization temperature and rheological and thermal properties of acrylonitrile (AN)-acrylamide (AM) copolymers. The copolymers were synthesized at different polymerization temperature. The copolymer structure was characterized by gel permeation chromatography (GPC) and Infrared spectrum (IR). The rheological and thermal properties were investigated by a viscometer and differential scanning calorimeter-thermogrametric (DSC-TG) analysis, respectively. When the polymerization temperature increased from $41^{\circ}C\;to\;65^{\circ}C$, the molecular weight $(\bar{M}_w)$ of copolymers decreased from 1,090,000 to 250,000, while its conversion increased from $18\%\;to\;63\%$, and the polymer composition changed slightly. To meet the requirements of carbon fibers, the rheological and thermal properties of products were also investigated. It was found that the relationship between viscosity and $\bar{M}_w$ was nonlinear and the viscosity index (n) decreased from 3.13 to 2.69, when the solution temperature increased from $30^{\circ}C\;to\;65^{\circ}C$. This suggests the dependence of viscosity upon $\bar{M}_w$ is higher at lower solution temperature. According to the result of activation energy, the sensivity of viscosity to solution temperature is higher for AN-AM copolymers synthesized at higher polymerization temperature. The result of thermal analysis shows that the copolymers obtained at higher polymerization temperature are easier to cyclization evidenced from lower initiation temperature. The weight loss behavior changed irregularly with polymerization temperature due to irregular change of liberation heat.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.357-362
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• 2003

The pathway producing imide ring closure during the thermal imidization of poly(amic acid) (PAA) was investigated in detail using a new analytical method, two-dimensional (2D) Raman correlation spectroscopy. The signs of the cross peaks in synchronous spectra provided evidence of the thermal imidization of PAA into PI as the heating temperature increased. The signs of the cross peaks in asynchronous spectra suggested that the imide-related modes changed prior to the amide or carboxylic mode, which indicates that cyclization occurred before the amide proton was abstracted.

• 폴리머
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• 제29권5호
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• pp.493-500
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• 2005

Poly(ethylene glycol)methyl ether(MPEG)와 dimethylphenoxy 팬던트 그룹을 갖는 polybenzoxazoles(PBOs)의 중합 전구체인 poly(o-hydroxyamides)(PHAs)를 저온 용액 중축합에 의해서 합성하였다. 합성된 중합 전구체들의 고유점도는 $0.51\~2.31$의 값을 나타내었다. 중합전구체는 FT-IR, $1H-NMR$, DSC, 그리고 TGA를 이용하여 특성을 조사하였다. MPEG단위를 갖는 PHAs는 MPEG의 분자량이 증가할수록 용매특성이 증가하는데, 특히 분자량이 1100인 MPEG를 갖는 PHA의 경우 aprotic 용매뿐만 아니라 에탄올, 메탄올, H,0에도 용해되었으나, 열적 고리화 반응에 의해 PBOs로 전환되면 어떠한 용매에도 용해되지 않았다. 그리고 MPEG만을 갖는 중합 전구체의 경우, MPEG의 분자량이 증가할수록 고리화 반응온도는 감소함을 확인할 수 있었다.

• Carbon letters
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• 제14권1호
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• pp.34-39
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• 2013

Acrylonitrile (AN)-acrylamide (AM) copolymers were prepared by nitric acidic hydrolysis of homopolyacrylonitrile. The acrylamino group increased as a function of hydrolysis time, while crystallinity decreased. Differential scanning calorimetry and a thermal gravimetric analysis indicated that the acylamino introduced by acidic hydrolysis effectively enhanced the cyclization reaction at low temperature due to the change of the cyclization reaction mechanism. Char-yield of AN-AM copolymers also gradually increased with increasing hydrolysis time. The maximum char-yield was 49.48% when hydrolized at $23^{\circ}C$ in 65% nitric acid solution for 18 h, which was 30% higher than that of non-acidic hydrolysis of homopolyacrylonitrile. Simulation of the practical process also showed an increase of char yields, where the char yields were 55.43% and 62.60% for homopolyacrylonitrile and copolyacrylonitrile, respectively, with a hydrolysis time of 13 h.

• Bulletin of the Korean Chemical Society
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• 제17권1호
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• pp.29-33
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• 1996

Mono-, or di-substituted chlorodicyanovinyl benzene compound was reacted with an excess amount of ethylenediamine to give corresponding imidazoline product with high reaction yield. This reaction occurs by stable imidazoline ring-forming process through nucleophilic attack of terminal amine on the enaminonitrile adduct, the reaction intermediate, toward electropositive enamine carbon, which is accompanied by the release of neutral malononitrile moiety. The similar reaction with 1,2-phenylenediamine produced stable enaminonitrile-amine adduct at lower temperature which could be cyclized intramolecularly to thermally stable benzimidazole at elevated temperature in solution or in solid state. From the difunctional compound of both reactants, poly(enaminonitrile-amine) could be prepared as a new soluble precursor polymer for well-known polybenzimidazole (PBI). The thermal cyclization reaction accompanying the release of malononitrile molecules was studied using thermalanalysis and infrared spectroscopy.

• Elastomers and Composites
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• 제53권3호
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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.

• 방사선산업학회지
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• 제6권1호
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• pp.55-59
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• 2012

Polyacrylonitrile (PAN)-based carbon fibers have been widely used due to their unique chemical, electrical, and mechanical properties. Electron beam irradiation has been extensively employed as means of altering properties of polymeric materials. Electron beam irradiation can induce chemical reactions in materials without any catalyst. Electron beam irradiation may be useful in accelerating the thermal compression stabilization of PAN nanofibers. To investigate the irradiation effect on PAN fibers, PAN nanofibers were irradiated by electron beam at 1,000~5,000 kGy. Irradiated and non-irradiated PAN nanofibers were heated at 180 and $220^{\circ}C$ without applying pressure for 15 min. Then 1 metric ton has been applied for 5 min. SEM images have been found that the fiber kept its morphological behavior after the hot pressing up to electron beam irradiated 1,000 kGy. DSC thermograms showed that the peak temperatures of the exothermic reactions were found to decrease with increasing electron beam irradiation doses and temperature. FT-IR spectra have been found to decrease $C{\equiv}N$ stretch band with increasing the electron beam irradiation dose. These results indicate that the modification of PAN via reactions such as cyclization is significantly enhanced by electron beam irradiation and thermal compression technique.

• Elastomers and Composites
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• 제43권4호
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• pp.271-280
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• 2008

고분자 주사슬에 벌키한 그룹과 ether 연결고리를 갖는 방향족 polyhydroxyamides (PHAs)를 저온 용액 중축합에 의해 합성하였다. FT-IR, $^{1}H-NMR$, DSC, 그리고 TGA를 이용하여 이 공중합체들의 특성을 조사하였다. 공중합체들은 열적 고리화 반응에 의해 polybenzoxazoles(PBOs)로 완전히 전환되었고, 흡열피크는 $220{\sim}400^{\circ}C$의 범위에서 관찰되었다. 주사슬에 에테르와 벌키한 그룹의 도입은 DMSO와 DMF와 같은 aprotic 용매들에서 PHAs의 용매특성을 향상시켰으나, PBOs는 어떠한 일반 용매에도 용해되지 않았다. 2,6-dimethyl phenoxy 팬던트와 2,3-dihydroxypyridine 고리를 갖는 PBO 5와 2,6-dimethylphenoxy 팬던트와 2,3-dihydroxyquinoxaline 고리를 갖는 PBO 6을 제외한 모든 PBOs는 $149{\sim}217^{\circ}C$ 영역에서 유리전이온도($T_g$)를 보였다. TGA 분석에서 대부분의 PBO들은 질소분위기하에서 $400^{\circ}C$까지 안정함을 보였다. 2,6-dimethylphenoxy 팬던트와 2,3-dihydroxypyridine 고리를 갖는 PHA 5와 PBO 5의 최대중량손실 온도는 각각 $707^{\circ}C$와 $683^{\circ}C$로 가장 높은 값을 보였다. PBOs는 질소분위기하의 $900^{\circ}C$에서 $63{\sim}70%$ 범위의 상대적으로 높은 차 수득율을 보였다.

• 한국산학기술학회논문지
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• 제14권5호
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• pp.2550-2558
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• 2013

주사슬에 oligo(oxy ethylene) 팬던트를 갖는 poly(o-hydroxyamides)(PHAs) 공중합체를 저온에서 용액 중축합 반응에 의해서 합성하였다. 이들 공중합 전구체들의 특성은 1H-NMR, FT-IR, DSC, TGA, UTM 그리고 LOI 등을 이용하여 조사하였다. $35^{\circ}C$의 DMAc 또는 DMAc/LiCl 용액하에서 측정된 PHAs의 고유점성도는 0.74~1.42 dL/g의 범위를 보였다. 전구체들의 용해도는 oligo(oxy ethylene) 단위의 증가와 함께 증가하였으나, polybenzexazoles(PBOs)는 다양한 용매에도 거의 용해되지 않았다. 공중합 전구체들의 분해온도는 질소분위기하에서 $408{\sim}664^{\circ}C$의 범위를 보였고, $900^{\circ}C$에서 char 수득률은 13~59%의 값을 보였다. 공중합 전구체들의 기계적 성질과 난연특성은 oligo(oxy ethylene) 단위가 증가함에 따라 감소하였다.