An efficient utilization strategy of ethylene tar(ET),the main by-product of the ethylene cracking unit,is urgently required to meet demands for modern petrochemical industry.On the other hand,condensed polynuclear ar...An efficient utilization strategy of ethylene tar(ET),the main by-product of the ethylene cracking unit,is urgently required to meet demands for modern petrochemical industry.On the other hand,condensed polynuclear aromatic resin of moderate condensation degree(B-COPNA)is a widely used carbon material due to its superb processability,the production of which is,however,seriously limited by the high cost of raw materials.Under such context,an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar(ETLF,boiling point<260℃)facilitated by molecular simulation.1,4-Benzenedimethanol(PXG)was first selected as the crosslinking agent according to the findings of molecular simulation.The effects of operating conditions,including reactions temperature,crosslinking agent,and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process.The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents.It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents.In addition to the highest yield and greatest heat properties,PXG-prepared resin contained the most condensed aromatics.The corresponding optimized conditions of resin preparation were 180℃,1:1.9(PXG:ETLF),and 3%(mass)of catalyst content with a resin yield of 78.57%.It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation,according to the experimental characterization and molecular simulation.Hence,it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation,bringing huge economic value to the current petrochemical industry.展开更多
The mechanism and kinetics of pyrolysis of condensed poly-nuclear aromatic(COPNA) resins were investigated by non-isothermal thermogravimetry/derivative thermogravimetry measurements at various heating rates(10, 20 an...The mechanism and kinetics of pyrolysis of condensed poly-nuclear aromatic(COPNA) resins were investigated by non-isothermal thermogravimetry/derivative thermogravimetry measurements at various heating rates(10, 20 and 30 K/min) in nitrogen atmosphere. The changes in the functional groups, microstructure, and elemental composition of COPNA resins heated to different temperatures(200, 400, and 600 ℃) were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, and elemental analysis, respectively. The results of the pyrolytic experiments indicated that the pyrolysis process could be divided into three stages: an initial weight loss stage ranging from 225—450 ℃, a second weight loss stage ranging from 450—560 ℃, and a thermally stable stage occurring above 560 ℃. The heating rate had little effect on the pyrolysis process, and thermogravimetric parameters of COPNA resin, such as temperature at initial weight loss stage(Ti), temperature at final weight loss stage(Tf) and temperature at maximum weight loss stage(Tmax), shifted towards higher temperatures when the heating rate was increased. At higher heating temperature, the number of aliphatic chains and substituted groups attached to aromatic rings of the resultant sample was reduced, whereas the C/H ratio and porosity rate increased. Pyrolysis kinetics studies showed that the activation energy(E) range for the first and second weight loss stages was 150—210 k J/mol and 210—275 k J/mol, respectively, which showed that the mechanism of thermal decomposition differed from that of the weight loss stages. The k0 value was in the orders of between 1011/s and 1018/s when the activation energy was less than 250 k J/mol. When the activation energiy was greater than 250 k J/mol, there was a linearly increasing relationship between k0 and E.展开更多
As an industrial byproduct of oil refining,furfural extract oil from reduced-pressure route Ⅱ with high aromatic content was used to prepare heat-resistant condensed polynuclear aromatic（COPNA） resin for the first ...As an industrial byproduct of oil refining,furfural extract oil from reduced-pressure route Ⅱ with high aromatic content was used to prepare heat-resistant condensed polynuclear aromatic（COPNA） resin for the first time.The basic properties of furfural extract oil and the resultant COPNA resin were characterized by infrared spectroscopy（FT-IR）,nuclear magnetic resonance spectroscopy（1H-NMR）,thermogravimetric analysis（TGA） and elemental analysis（EA）.The result showed that heat treated furfural extract oil was successfully used for the synthesis of heat-resistant COPNA resin.The average structural parameters of raw materials and prepared resin were calculated by the improved Brown-Ladner method,and the averaged molecular structure of the resin was obtained.The reaction mechanism for the synthesis of COPNA resin was suggested as an acid-catalyzed positive ion type polymerization.展开更多
A bisphenol epoxy resin was used as modifier to increase the heat resistance of condensed poly-nuclear aromatic （COPNA） resin. The basic properties of COPNA resin and modified resin were characterized by Fourier tra...A bisphenol epoxy resin was used as modifier to increase the heat resistance of condensed poly-nuclear aromatic （COPNA） resin. The basic properties of COPNA resin and modified resin were characterized by Fourier transform infrared spectroscopy （FT-IR）, nuclear magnetic resonance spectroscopy （1H-NMR）, vapor pressure osmometry （VPO） and elemental analysis （EA）. Average structural parameters of resins were calculated by the improved Brown-Ladner method, and heat resistance of resins was tested by thermogravimetric analysis （TGA）. The chemical structure, mechanical properties and heat resistivity of the resin/graphite composites prepared with different resins were compared. The results show that the adhesive property and heat resistance of COPNA resin can be remarkably improved by addition of 5 wt.% epoxy resin. The reason is that the reactions between epoxy groups of epoxy resin and hydroxyl groups of COPNA resin improve the heat resistance and adhesive property of COPNA resin. Electric motor brushes with good mechanical properties and low electrical resistivity were successfully prepared by using the modified resin as binder.展开更多
基金support of National Natural Science Foundation of P.R.China(22308104).
文摘An efficient utilization strategy of ethylene tar(ET),the main by-product of the ethylene cracking unit,is urgently required to meet demands for modern petrochemical industry.On the other hand,condensed polynuclear aromatic resin of moderate condensation degree(B-COPNA)is a widely used carbon material due to its superb processability,the production of which is,however,seriously limited by the high cost of raw materials.Under such context,an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar(ETLF,boiling point<260℃)facilitated by molecular simulation.1,4-Benzenedimethanol(PXG)was first selected as the crosslinking agent according to the findings of molecular simulation.The effects of operating conditions,including reactions temperature,crosslinking agent,and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process.The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents.It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents.In addition to the highest yield and greatest heat properties,PXG-prepared resin contained the most condensed aromatics.The corresponding optimized conditions of resin preparation were 180℃,1:1.9(PXG:ETLF),and 3%(mass)of catalyst content with a resin yield of 78.57%.It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation,according to the experimental characterization and molecular simulation.Hence,it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation,bringing huge economic value to the current petrochemical industry.
基金supported by the National Natural Science Foundation of China(511572296)the Fundamental Research Funds for the Central Universities(15CX02084A)
文摘The mechanism and kinetics of pyrolysis of condensed poly-nuclear aromatic(COPNA) resins were investigated by non-isothermal thermogravimetry/derivative thermogravimetry measurements at various heating rates(10, 20 and 30 K/min) in nitrogen atmosphere. The changes in the functional groups, microstructure, and elemental composition of COPNA resins heated to different temperatures(200, 400, and 600 ℃) were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, and elemental analysis, respectively. The results of the pyrolytic experiments indicated that the pyrolysis process could be divided into three stages: an initial weight loss stage ranging from 225—450 ℃, a second weight loss stage ranging from 450—560 ℃, and a thermally stable stage occurring above 560 ℃. The heating rate had little effect on the pyrolysis process, and thermogravimetric parameters of COPNA resin, such as temperature at initial weight loss stage(Ti), temperature at final weight loss stage(Tf) and temperature at maximum weight loss stage(Tmax), shifted towards higher temperatures when the heating rate was increased. At higher heating temperature, the number of aliphatic chains and substituted groups attached to aromatic rings of the resultant sample was reduced, whereas the C/H ratio and porosity rate increased. Pyrolysis kinetics studies showed that the activation energy(E) range for the first and second weight loss stages was 150—210 k J/mol and 210—275 k J/mol, respectively, which showed that the mechanism of thermal decomposition differed from that of the weight loss stages. The k0 value was in the orders of between 1011/s and 1018/s when the activation energy was less than 250 k J/mol. When the activation energiy was greater than 250 k J/mol, there was a linearly increasing relationship between k0 and E.
基金financially supported by the National Natural Science Foundation of China (Nos. 20876176, 51172285, 51372277)the Natural Science Foundation of Shandong Province (ZR2011EL030)the Fundamental Research Funds for the Central Universities (14CX02060A)
文摘As an industrial byproduct of oil refining,furfural extract oil from reduced-pressure route Ⅱ with high aromatic content was used to prepare heat-resistant condensed polynuclear aromatic（COPNA） resin for the first time.The basic properties of furfural extract oil and the resultant COPNA resin were characterized by infrared spectroscopy（FT-IR）,nuclear magnetic resonance spectroscopy（1H-NMR）,thermogravimetric analysis（TGA） and elemental analysis（EA）.The result showed that heat treated furfural extract oil was successfully used for the synthesis of heat-resistant COPNA resin.The average structural parameters of raw materials and prepared resin were calculated by the improved Brown-Ladner method,and the averaged molecular structure of the resin was obtained.The reaction mechanism for the synthesis of COPNA resin was suggested as an acid-catalyzed positive ion type polymerization.
基金supported by the National Natural Science Foundation of China (Nos. 51172285, 51372277)the Fundamental Research Funds for the Central Universities (14CX02060A)the Natural Science Foundation of Shandong Province (ZR2011EL030)
文摘A bisphenol epoxy resin was used as modifier to increase the heat resistance of condensed poly-nuclear aromatic （COPNA） resin. The basic properties of COPNA resin and modified resin were characterized by Fourier transform infrared spectroscopy （FT-IR）, nuclear magnetic resonance spectroscopy （1H-NMR）, vapor pressure osmometry （VPO） and elemental analysis （EA）. Average structural parameters of resins were calculated by the improved Brown-Ladner method, and heat resistance of resins was tested by thermogravimetric analysis （TGA）. The chemical structure, mechanical properties and heat resistivity of the resin/graphite composites prepared with different resins were compared. The results show that the adhesive property and heat resistance of COPNA resin can be remarkably improved by addition of 5 wt.% epoxy resin. The reason is that the reactions between epoxy groups of epoxy resin and hydroxyl groups of COPNA resin improve the heat resistance and adhesive property of COPNA resin. Electric motor brushes with good mechanical properties and low electrical resistivity were successfully prepared by using the modified resin as binder.
