A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differentia...A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.展开更多
The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out ...The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)4]were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO(or TPA)with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.展开更多
2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the t...2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.展开更多
The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent...The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.展开更多
The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were ...The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.展开更多
[目的]3-(3′,4′-次甲二氧苯基)-N-正丙基丙烯酰胺是具有广谱抑菌活性的化合物,将其研制成优良环保剂型悬浮剂,可为实现田间应用提供技术依据。[方法]采用湿法研磨制备了12种不同配方的悬浮剂,通过质量指标检测确定最佳配方,测定其表...[目的]3-(3′,4′-次甲二氧苯基)-N-正丙基丙烯酰胺是具有广谱抑菌活性的化合物,将其研制成优良环保剂型悬浮剂,可为实现田间应用提供技术依据。[方法]采用湿法研磨制备了12种不同配方的悬浮剂,通过质量指标检测确定最佳配方,测定其表面张力及其在黄瓜叶面的动态接触角,并开展了防治黄瓜白粉病田间药效试验。[结果]最佳配方为3-(3′,4′-次甲二氧苯基)-N-正丙基丙烯酰胺40%(折百)、S043%、D4252%、W071%、乙二醇3%、硅酸镁铝0.4%、黄原胶0.12%、B150.12%、消泡剂X600.3%、水补足。此悬浮剂在有效成分0.27 g a.i./L时的表面张力以及在黄瓜叶面的动态接触角均小于对照药剂40%苯醚甲环唑SC,表明其具有良好的润湿性能。在有效成分0.27 g a.i./L下的防效为88.38%,与对照药剂25%嘧菌酯SC 0.20 g a.i./L相当,且对黄瓜安全。[结论]制备悬浮剂为类白色均匀悬浮液,流动性好,粒径合格,悬浮率稳定在98.5%左右,pH为4.09,黏度为452 mPa·s,入水分散性合格,热储、低温及冻融稳定性良好,未出现沉淀,各项指标均达标,对黄瓜白粉病防效优良,具有良好的开发应用前景。展开更多
基金Supported by Research Funds from Chinese Education Department (2003406)Bureau of Science and Technology of Jiangsu Province (BG2006025)
文摘A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.
文摘The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)4]were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO(or TPA)with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.
基金Supported by the National "973" project (No. 613740102)
文摘2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.
基金Supported by the National Natural Science Foundation of China(21673132).
文摘The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.
基金supported by the Foundation of Liaoning Provincial Department of Education (990321076)
文摘The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.
文摘[目的]3-(3′,4′-次甲二氧苯基)-N-正丙基丙烯酰胺是具有广谱抑菌活性的化合物,将其研制成优良环保剂型悬浮剂,可为实现田间应用提供技术依据。[方法]采用湿法研磨制备了12种不同配方的悬浮剂,通过质量指标检测确定最佳配方,测定其表面张力及其在黄瓜叶面的动态接触角,并开展了防治黄瓜白粉病田间药效试验。[结果]最佳配方为3-(3′,4′-次甲二氧苯基)-N-正丙基丙烯酰胺40%(折百)、S043%、D4252%、W071%、乙二醇3%、硅酸镁铝0.4%、黄原胶0.12%、B150.12%、消泡剂X600.3%、水补足。此悬浮剂在有效成分0.27 g a.i./L时的表面张力以及在黄瓜叶面的动态接触角均小于对照药剂40%苯醚甲环唑SC,表明其具有良好的润湿性能。在有效成分0.27 g a.i./L下的防效为88.38%,与对照药剂25%嘧菌酯SC 0.20 g a.i./L相当,且对黄瓜安全。[结论]制备悬浮剂为类白色均匀悬浮液,流动性好,粒径合格,悬浮率稳定在98.5%左右,pH为4.09,黏度为452 mPa·s,入水分散性合格,热储、低温及冻融稳定性良好,未出现沉淀,各项指标均达标,对黄瓜白粉病防效优良,具有良好的开发应用前景。
文摘目的:观察葛根芩连汤辅助0.1%糠酸莫米松乳膏及盐酸西替利嗪片治疗特应性皮炎(Atopic dermatitis,AD)患者的临床疗效以及血清中神经生长因子(Nerve growth factor,NGF)和神经营养因子4(Neurotrophin-4,NT-4)水平的影响。方法:选取2021年5月-2023年5月收入笔者医院的AD患者60例,根据治疗方案的差异随机分为对照组(西药治疗)、观察组(西药治疗+中药辅助治疗)每组30例。对照组采用外用糠酸莫米松乳膏,口服盐酸西替利嗪进行干预治疗,观察组在对照组基础上采用葛根芩连汤辅助进行治疗。观察两组患者治疗前、后血清中NGF、NT-4水平、瘙痒视觉模拟评分(Visual analogue scale,VAS)、湿疹面积及严重指数(Eczema area and severity index,EASI)评分,治疗后临床疗效及不良反应发生率。结果:治疗前两组患者血清中NGF、NT-4水平、VAS评分、EASI评分相比差异无统计学意义(P>0.05),经治疗后两组患者血清中NGF、NT-4水平、VAS评分、EASI评分均较同组治疗前显著降低(P<0.05),且观察组优于对照组(P<0.05);经治疗后,观察组患者临床疗效总有效率高于对照组,不良反应发生率低于对照组(P<0.05)。结论:葛根芩连汤辅助西药治疗AD可下调患者血清中NGF、NT-4水平,减轻瘙痒症状及皮损程度,改善临床症状,降低不良事件的发生率,值得临床推广应用。
