Homogeneous isotropic pitches with high softening points were prepared from vacuum-distilled heavy residue ethylene tar(ET-HR)by a two-step method of bromination and subsequent dehydrobromination/polycondensation.The ...Homogeneous isotropic pitches with high softening points were prepared from vacuum-distilled heavy residue ethylene tar(ET-HR)by a two-step method of bromination and subsequent dehydrobromination/polycondensation.The ET-HR was first brominated at 30 or 200℃,and then heat-treated at 350℃to enable the dehydrobromination/polycondensation reactions.GC/MS and LDI TOF/MS spectra indicated that the ET-HR was mainly composed of compounds containing 3-to 6-ring aromatic species with a considerable aliphatic chain content.Compared with thermal condensation alone,such a two-step method increased the softening point of the pitches from 152 to 264℃with a yield in the range of 62 wt.%-67 wt.%and a coking value in the range of 57 wt.%-77 wt.%,depending on the bromination temperature and the bromine content.Structural characterization of the as-prepared pitches by elemental analysis,1H NMR,FT-IR and LDI-TOF/MS showed increased aromatization and polymerization of the precursor during the dehydrobrominatio/polycondensation.All the homogeneous isotropic pitches showed an ability to transform into an anisotropic texture after coking at 800℃.展开更多
Tetrahydrofuran(THF) extract of coal tar pitch(CTP) was used instead of blending CTP with pretreated pyrolysis fuel oil to prepare an isotropic pitch precursor with excellent spinnability for general-purpose carbon fi...Tetrahydrofuran(THF) extract of coal tar pitch(CTP) was used instead of blending CTP with pretreated pyrolysis fuel oil to prepare an isotropic pitch precursor with excellent spinnability for general-purpose carbon fibre through bromination-dehydrobromination. The feasibility and effectiveness of synthesising an isotropic pitch precursor derived from THF-soluble(CTP-THFs) is demonstrated in this study.The results show that CTP-THFs contains more light components than CTP;CTP-THFs and CTP monomer proportions were 62.52% and 45.32%, respectively. However, based on comparisons of CTP-THFsBr0 and CTPBr0 characterisations, CTP-THFs exhibits better polycondensation than CTP. Bromination-dehydrobro mination promotes polycondensation of pitch precursors, leading to greater carbon aromaticity in CTP-THFsBr5, CTP-THFsBr10, and CTP-THFsBr15 than that in CTP-THFsBr0 and CTPBr0. CTP-THFsBr5 and CTP-THFsBr10 have excellent spinnability even with softening points as high as 230 ℃. The pericondensed carbon and carbon aromaticity of CTP-THFsBr5 and CTP-THFsBr10 are high owing to the higher degree of polycondensation;however, they still possess a more linear molecular structure. The as-prepared carbon fibre exhibits homogeneity and uniformity, and the mechanical performance is comparable with that of commercial general-purpose carbon fibre products.展开更多
Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoate...Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoates produced are hydrolysed in situ and the corresponding acids are obtained after mostly simple extractive work-up, often without employing organic solvents. Under the same conditions, benzaldehydes are reacted with alkoxycarbonyl bromomethy-lidenephosphorane to produce 3-arylprop-2-ynoic acids (arylpropiolic acids).展开更多
文摘Homogeneous isotropic pitches with high softening points were prepared from vacuum-distilled heavy residue ethylene tar(ET-HR)by a two-step method of bromination and subsequent dehydrobromination/polycondensation.The ET-HR was first brominated at 30 or 200℃,and then heat-treated at 350℃to enable the dehydrobromination/polycondensation reactions.GC/MS and LDI TOF/MS spectra indicated that the ET-HR was mainly composed of compounds containing 3-to 6-ring aromatic species with a considerable aliphatic chain content.Compared with thermal condensation alone,such a two-step method increased the softening point of the pitches from 152 to 264℃with a yield in the range of 62 wt.%-67 wt.%and a coking value in the range of 57 wt.%-77 wt.%,depending on the bromination temperature and the bromine content.Structural characterization of the as-prepared pitches by elemental analysis,1H NMR,FT-IR and LDI-TOF/MS showed increased aromatization and polymerization of the precursor during the dehydrobrominatio/polycondensation.All the homogeneous isotropic pitches showed an ability to transform into an anisotropic texture after coking at 800℃.
基金the financial support provided by the National Natural Science Foundation of China (22008254)the Fundamental Research Funds for the Central Universities (2020XJHH01)+1 种基金the National Training Program of Innovation and Entrepreneurship for Undergraduates (C202003309)China University of Mining and Technology (Beijing) Yueqi Outstanding Scholar Project (2020JCB02)。
文摘Tetrahydrofuran(THF) extract of coal tar pitch(CTP) was used instead of blending CTP with pretreated pyrolysis fuel oil to prepare an isotropic pitch precursor with excellent spinnability for general-purpose carbon fibre through bromination-dehydrobromination. The feasibility and effectiveness of synthesising an isotropic pitch precursor derived from THF-soluble(CTP-THFs) is demonstrated in this study.The results show that CTP-THFs contains more light components than CTP;CTP-THFs and CTP monomer proportions were 62.52% and 45.32%, respectively. However, based on comparisons of CTP-THFsBr0 and CTPBr0 characterisations, CTP-THFs exhibits better polycondensation than CTP. Bromination-dehydrobro mination promotes polycondensation of pitch precursors, leading to greater carbon aromaticity in CTP-THFsBr5, CTP-THFsBr10, and CTP-THFsBr15 than that in CTP-THFsBr0 and CTPBr0. CTP-THFsBr5 and CTP-THFsBr10 have excellent spinnability even with softening points as high as 230 ℃. The pericondensed carbon and carbon aromaticity of CTP-THFsBr5 and CTP-THFsBr10 are high owing to the higher degree of polycondensation;however, they still possess a more linear molecular structure. The as-prepared carbon fibre exhibits homogeneity and uniformity, and the mechanical performance is comparable with that of commercial general-purpose carbon fibre products.
文摘Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoates produced are hydrolysed in situ and the corresponding acids are obtained after mostly simple extractive work-up, often without employing organic solvents. Under the same conditions, benzaldehydes are reacted with alkoxycarbonyl bromomethy-lidenephosphorane to produce 3-arylprop-2-ynoic acids (arylpropiolic acids).
