Alkylated 2,2′-bithiophenes and 2-phenylthiophenes in the composition of pyrolysis products of high-sulfur kerogen

Compounds from the 5-n-alkyl-2,2′-bithiophene, 5-n-alkyl-5′-methyl-2,2′-bithiophene, 5-n-alkyl-2-phenylthiophene, and 5-n-alkyl-2-o-tolylthiophene homologous series were synthesized to prove their presence in the pyrolysis products of sulfur-rich kerogen. A study of the pyrolysis products of sulfur-vulcanized polybutadiene confirmed that these compounds can be formed via the thermal transformation of n-alkyl polysulfur-bound fragments of sulfur-rich kerogen. The earlier proposed scheme that assumes the dependence of the composition of the pyrolysis products of sulfur-rich kerogen on its saturation with sulfide bridges was experimentally corroborated.     

Theoretical Study of 2,4,6-Tris(3′,5′-Diamino-2′,4′,6′-Trinitrophenylamino)-1,3,5-Triazine

The density functional theory (DFT) BLYP and B3LYP method with 3–21G* and 6–31G** basis sets were used to predict the structures, natural bond orbital (NBO) atomic charges, and ring interactions of 2,4,6-tris(3′,5′-diamino-2′,4′,6′-trinitrophenylamino)-1,3,5-triazine (PL-1). Approximately, the molecule possesses C₃ symmetry with three benzene rings tilted to the triazine plane. The interactions among three 3′,5′-diamino-2′,4′,6′-trinitrophenylamino groups are of additivity. The heat of formation of PL-1 was estimated to be 427.6 J/mol via isodesmic reaction. Detonation velocity and pressure are 8.5 km/s and 35.5 GPa, respectively.     

Binary mixtures of heavy metal chelates with N,N,N′,N′-tetrasubstituted p-phenylenediamines in inhibition of ethylbenzene oxidation

Synergy was revealed in the action of binary mixtures of heavy metal chelates with N,N,N′,N′-tetrasubstituted p-phenylenediamines in the initiated oxidation of model hydrocarbon ethylbenzene. The value of the synergistic effect (SE), defined as SE = (W _add/W _mix) ? 1, where W _mix and W _add are the initial rates of oxygen uptake as obtained experimentally and calculated on the assumption of the additive action of the mixture components, respectively, increases with a decrease in the half-wave potential of the one-electron electrochemical oxidation E ₁ ^2/ox of both chelates and tertiary diamines.     

Burning Characteristics of Aminoguanidinium 5,5′-Azobis-1H-Tetrazolate/Ammonium Nitrate Mixture—Effects of Particle Size and Composition Ratio on Burning Rate

Ammonium nitrate has been attracting attention over the years as an oxidizer for clean gas-generating agents. Aminoguanidinium 5,5′-azobis-1H-tetrazolate was mixed with ammonium nitrate to improve its burning performance and the burning behavior of the formulations was studied by measuring the linear burning rate. The effects of particle size and composition ratio on the burning rate were studied. It was found that the mixture containing 50% ammonium nitrate by weight was the most promising composition. The particle sizes of fuel and oxidizer do not influence the burning rate.     

2,2′,7,7′-四溴-9,9′-螺二芴的合成

以2-溴联苯的Grignard试剂和9-芴酮反应制备9-(2-联苯基)-9-芴醇,经关环反应制备了9,9′-螺二芴(SBF),并以溴化钠为溴源、过氧化氢为氧化剂、1,2-二氯乙烷为溶剂,通过SBF的氧化溴化反应制备了2,2′,7,7′-四溴-9,9′-螺二芴(TBSBF)。采用质谱、核磁共振对SBF和TBSBF的结构进行了表征,并用高效液相色谱仪测定了SBF和TBSBF的含量;考察了反应物配比、反应时间、反应温度和溶剂种类对氧化溴化合成TBSBF反应的影响。确定了较佳的工艺条件为:n(SBF)∶n(溴化钠)∶n(过氧化氢)∶n(硫酸)=1∶8∶6∶6,溶剂为1,2-二氯乙烷,反应温度20℃,反应时间48h。在此条件下,TBSBF的选择性达到95.1%,产物TBSBF纯度大于98%,收率约为80%。     

3,3′,5,5′-四甲基-4,4′-联苯二醌的合成

以 2 ,6-二甲基苯酚、氧气为原料 ,氨水与乙酸铜为催化剂 ,合成得到了 3 ,3′,5 ,5′ -四甲基 -4 ,4′-联苯二醌 ,得到反应的最佳条件为 :2 ,6-二甲基苯酚的浓度为 0 .1g/mL ,氨水与乙酸铜的摩尔比为 0 .43 ,温度为 75℃ ,反应时间为 6h ,产率达到 60 %。     

光致变色材料2,2′-双(2,4-二氯苯基)-4,4′,5,5′-四苯基-1,2′-联咪唑的合成研究

以联苯甲酰、2 ,4-二氯苯甲醛为原料 ,经过环合、氧化合成了一种光致变色材料 2 ,2′-双 (2 ,4-二氯苯基 ) -4,4′,5 ,5′-四苯基 -1 ,2′-联咪唑。研究了多种因素对氧化反应收率的影响 ,其最佳工艺条件为 :以乙二醇一乙醚为分散剂 ,单体 2 -(2 ,4-二氯苯基 ) -4,5 -二苯基咪唑与氧化剂 K3[Fe(CN) 6 ]的摩尔比为 :1∶ 2 .5 ,反应温度0～ 1 0℃ ,反应时间 4h,总收率为 84.5 % (以 2 ,4-二氯苯甲醛计 )     

新鲜铜粉“一锅法”催化Ullmann缩合反应制备4,4′-二氨基-1,1′-二蒽醌-3,3′-二磺酸钠

研究了用次亚磷酸钠现场液相还原硫酸铜制备新鲜铜粉,用该铜粉"一锅法"催化溴氨酸的自身Ullmann缩合反应制备4,4′-二氨基-1,1′-二蒽醌-3,3′-二磺酸钠。适宜的反应条件是:20.0g五水硫酸铜,5.8g EDTA,20.4g次亚磷酸钠,还原温度70℃,5.0g溴氨酸,缩合反应温度90℃,缩合反应时间3h,缩合产物收率可达到97.9%。     

4,4′-二羟基二苯砜的研制

研究了由苯酚与浓硫酸在高温下缩合制备4,4′-二羟基二苯砜(双酚S)的工艺。利用高效液相色谱仪对反应过程进行监测,确定了合成双酚S的最佳反应条件和比较经济的提纯方法。利用该方法,原料硫酸的转化率高于76％,未反应苯酚通过蒸馏回收利用,提纯过程中产物损失较少。制得产品的纯度在98.5％以上,熔点为249℃。     

4,4′-二羟基二苯砜的研制

研究了由苯酚与浓硫酸在高温下缩合制备4,4′-二羟基二苯砜(双酚S)的工艺。利用高效液相色谱仪对反应过程进行监测,确定了合成双酚S的最佳反应条件和比较经济的提纯方法。利用该方法,原料硫酸的转化率高于76％,未反应苯酚通过蒸馏回收利用,提纯过程中产物损失较少。制得产品的纯度在98.5％以上,熔点为249℃。     

Synthesis and characterization of 2,4,6-tris (3′, 5′-diamino-2′,4′,6′-trinitrophenylamino)-1,3,5-triazine (PL-1): A new thermally stable insensitive high explosive

Abstract

2,4,6-tris (3′,5′-diamino-2′,4′,6′-trinitrophenylamino)-1,3,5-triazine (PL-1). has been synthesized in 29—31% overall yield from cyanuric chloride and 3,5-dichloroaniline following condensation, nitration and amination reactions. The structure of the compound has been assigned on the basis of spectral data (IR, ¹H-NMR and Mass) and elemental analysis. Some of the physico-chemical and explosive properties including thermal behaviour of the compound are also reported.     

2，2′-二氯氢化偶氮苯重排生成3，3′-二氯联苯胺的研究

采用Pd／C催化剂催化邻硝基氯苯加氢，制得2，2′-二氯氢化偶氮苯（DHB），再经过重排反应得到3，3′-二氯联苯胺（DCB）。研究了反应温度、硫酸质量分数和用量、反应时间等因素对重排反应的影响规律，确定了最佳重排反应条件，即反应温度0．5℃、硫酸质量分数50％、硫酸与DHB的摩尔比7：1、反应时间4h。在最佳条件下，产物3，3′-二氯联苯胺盐酸盐的收率为80％．83％，总氨基值大于95．0％。     

塔里木盆地深层沉积物石英E′心热力学特性

热活化技术通常以石英E′心的信号强度代替石英氧空位心的相对浓度,测定石英E′心的寿命时也使用热活化技术.在进行塔里木盆地TK301井深层(深度4895～5102m)二叠系沉积物的ESR研究时,发现石英E′心的信号经300℃热活化30min后不见增长,直至500℃时才显著减少.这一观测结果和Toyoda的实验结论相一致,表明尽管石英氧空位的形成效率比较低,但是在环境物质的β和γ剂量长时间辐射作用下可以生成氧空位心.在深层沉积物的ESR测年实验中,可以直接用石英E′心的ESR信号代替氧空位心的相对浓度.图1表1参7(业渝光摘)     

2007中国石油贸易峰会（CoTS′2007）

回首2006，国际石油价格上半年屡新高，下半年则单边下挫，全年走势跌宕起伏。展望2007，石油行惰将振荡下行，还是再续辉煌？     

4,4′-二氨基二苯醚的合成研究进展

介绍了4，4′-二氨基二苯醚合成方法的研究进展，阐述了其工艺条件。经过分析比较，认为以对硝基氯苯为原料用改进的一步缩合法合成4，4′-二硝基二苯醚中间体，然后再催化加氢得到4，4′-二氨基二苯醚是较好的合成路线。