Abstract
A novel methylene-bridged polymeric pitch was successfully synthesized from 1-methylnaphthalene (1-MNP) using bromine as a sacrificial agent for C-C bond construction. 1-MNP was reacted with bromine in the presence of strong visible light irradiation (40-70 kcal/mol), yielding exclusively side-chain substituted 1-methylnaphthalene (M-Br). After a thermal dehydrobromination/polycondensation reaction at 200-270 °C, high quality carbonaceous isotropic pitches with a softening point of 196-250 °C were obtained. The optimized factors influencing the photobromination, including reaction temperature, substrate concentration and properties of solvents were determined. The dehydrobromination reaction kinetic followed a pseudo-first-order reaction model with apparent reaction activation energy of 122.6 kJ/mol. The as-prepared polymeric pitches consisted of numbers of repeated monomers with a linear structure of methylene bridged naphthalene rings. The unique structure of the pitches resulted in high value of C/H ratio, high molecular weight and 100% soluble in toluene. Moreover, the pitches exhibited very low viscosity at temperatures near the softening point, and their viscosities experienced a unique transition from shear-thinning to shear-thickening and then to shear-thinning process. The coke obtained from short molecular pitch by carbonizing at 550 °C show an anisotropic phase of flow domains both in atmospheric pressure and pressured conditions.
| Original language | English |
|---|---|
| Pages (from-to) | 780-788 |
| Number of pages | 9 |
| Journal | Carbon |
| Volume | 95 |
| DOIs | |
| Publication status | Published - Oct 11 2015 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
Synthesis and characterization of high-softening-point methylene-bridged pitches by visible light irradiation assisted free-radical bromination. / Ge, Chuanzhang; Yang, Haixiao; Miyawaki, Jin; Mochida, Isao; Yoon, Seong-Ho; Qiao, Wenming; Long, Donghui; Ling, Licheng.
In: Carbon, Vol. 95, 11.10.2015, p. 780-788.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis and characterization of high-softening-point methylene-bridged pitches by visible light irradiation assisted free-radical bromination
AU - Ge, Chuanzhang
AU - Yang, Haixiao
AU - Miyawaki, Jin
AU - Mochida, Isao
AU - Yoon, Seong-Ho
AU - Qiao, Wenming
AU - Long, Donghui
AU - Ling, Licheng
PY - 2015/10/11
Y1 - 2015/10/11
N2 - A novel methylene-bridged polymeric pitch was successfully synthesized from 1-methylnaphthalene (1-MNP) using bromine as a sacrificial agent for C-C bond construction. 1-MNP was reacted with bromine in the presence of strong visible light irradiation (40-70 kcal/mol), yielding exclusively side-chain substituted 1-methylnaphthalene (M-Br). After a thermal dehydrobromination/polycondensation reaction at 200-270 °C, high quality carbonaceous isotropic pitches with a softening point of 196-250 °C were obtained. The optimized factors influencing the photobromination, including reaction temperature, substrate concentration and properties of solvents were determined. The dehydrobromination reaction kinetic followed a pseudo-first-order reaction model with apparent reaction activation energy of 122.6 kJ/mol. The as-prepared polymeric pitches consisted of numbers of repeated monomers with a linear structure of methylene bridged naphthalene rings. The unique structure of the pitches resulted in high value of C/H ratio, high molecular weight and 100% soluble in toluene. Moreover, the pitches exhibited very low viscosity at temperatures near the softening point, and their viscosities experienced a unique transition from shear-thinning to shear-thickening and then to shear-thinning process. The coke obtained from short molecular pitch by carbonizing at 550 °C show an anisotropic phase of flow domains both in atmospheric pressure and pressured conditions.
AB - A novel methylene-bridged polymeric pitch was successfully synthesized from 1-methylnaphthalene (1-MNP) using bromine as a sacrificial agent for C-C bond construction. 1-MNP was reacted with bromine in the presence of strong visible light irradiation (40-70 kcal/mol), yielding exclusively side-chain substituted 1-methylnaphthalene (M-Br). After a thermal dehydrobromination/polycondensation reaction at 200-270 °C, high quality carbonaceous isotropic pitches with a softening point of 196-250 °C were obtained. The optimized factors influencing the photobromination, including reaction temperature, substrate concentration and properties of solvents were determined. The dehydrobromination reaction kinetic followed a pseudo-first-order reaction model with apparent reaction activation energy of 122.6 kJ/mol. The as-prepared polymeric pitches consisted of numbers of repeated monomers with a linear structure of methylene bridged naphthalene rings. The unique structure of the pitches resulted in high value of C/H ratio, high molecular weight and 100% soluble in toluene. Moreover, the pitches exhibited very low viscosity at temperatures near the softening point, and their viscosities experienced a unique transition from shear-thinning to shear-thickening and then to shear-thinning process. The coke obtained from short molecular pitch by carbonizing at 550 °C show an anisotropic phase of flow domains both in atmospheric pressure and pressured conditions.
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U2 - 10.1016/j.carbon.2015.09.003
DO - 10.1016/j.carbon.2015.09.003
M3 - Article
VL - 95
SP - 780
EP - 788
JO - Carbon
JF - Carbon
SN - 0008-6223
ER -