Cu(NH3)2(FOX-7)2的晶体结构和热行为

用l,1-二氨基-2,2-二硝基乙烯的钾盐[K(FOX-7)·H2O]和硝酸铜在氨水体系中合成了Cu( NH3)2(FOX-7)2,并培养得到了单晶.该晶体为单斜晶系,空间群P21/c,a=0.68818(7)nm,b=O.73083 (8) nm,c=1.319 66(14)nm,β=95.986°,V=0.6600...     

盐酸氨基脲的分子结构及热分解特性

培养得到了盐酸氨基脲单晶，用X-射线单晶衍射分析、元素分析以及红外光谱分析对盐酸氨基脲的分子结构进行了表征。结果表明，盐酸氨基脲是离子型化合物，其晶体属于正交晶系，P212121空间群；晶体学参数为a=0．4672(1)nm，6=0．7547(1)nm，c=1．3209(2)nm；V=0．4657(9)nm^3，Z=4；Dr=1．591g／cm^3；F(000)=232。用DSC和TG-DTG分析技术研究了热分解过程，结果表明，盐酸氨基脲受热时存在一个吸热熔化过程和3个连续的放热分解、失重过程，加热至400℃时完全分解成气体产物。     

3,6-二氨基-1,2,4,5-四嗪的百克量合成、晶体结构和热行为

以3,6-双(3,5-二甲基吡唑)-1,2,4,5-四嗪为原料,合成了3,6-二氨基-1,2,4,5-四嗪(DATz),产率为98.7%,合成量为500g/批。采用核磁、红外光谱、质谱和元素分析等对产物的结构进行了表征。在N-甲基吡咯烷酮和水的混合溶剂中培养了DATz的单晶,用X-射线单晶衍射仪测定了晶体结构。采用DSC、TG-DTG和固体原位反应池/FT-IR联用等分析方法研究了DATz的热分解行为。结果表明,该晶体为正交晶系,属Cmcm空间群,晶体学参数为:a=0.9431(4)nm,b=0.7850(3)nm,c=0.6267(3)nm,V=0.464(3)nm3,Z=8,Dc=1.605g/cm3,μ=0.123mm-1,F(000)=232,R1=0.0407,wR2=0.1278。DATz的放热分解峰温度为342.17℃,热稳定性较好,可能的热分解机理为先发生四嗪环的开环反应,后进行取代基氨基的分解反应。     

含CL-20、DNTF和FOX-12的CMDB推进剂的热分解

用PDSC研究了添加CL-20（或DNTF或FOX-12）的改性双基推进剂的热分解行为.发现PDSC曲线中CL-20、DNTF推进剂有两个放热峰,第一个为双基黏结剂的分解峰,第二个为CL-20或DNTF的分解峰.FOX-12改性双基推进剂只有一个分解峰,表明FOX-12和双基黏结剂（NC、NG等组分）一起分解.     

三羟甲基丙烷三硝酸酯的热分解性能

利用高压DSC研究了三羟甲基丙烷三硝酸酯(TMPTN)的热分解特性.结果表明,尽管TMPTN与硝化甘油(NG)和三羟甲基乙烷三硝酸酯(TMETN)的结构相似,但TMPTN的热分解特性完全不同于NG和TMETN.常压下, TMPTN有两个峰,一个是熔化吸热峰,另一个是分解放热峰,而NG则是一个熔化吸热峰,TMETN是一个分解放热峰,没有熔化吸热峰;在高压下, TMPTN也有一个熔化吸热峰和一个分解放热峰,只是熔化吸热峰相对没有常压下的明显,随着压力的不同,峰形、峰温、放热量都明显不同.同时对TMPTN的分解机理进行了初步分析,并获得了TMPTN的热分解反应动力学参数.     

4,5-二氧代氰基咪唑盐酸盐的合成与表征

以4,5-二氰基咪唑为起始原料,通过羟胺氰基加成、重氮化取代、水解脱氯化氢等反应自主设计、合成了新型含能化合物4,5-二氧代氰基咪唑盐酸盐,总收率为58.2%;利用红外、核磁和元素分析等方法对目标化合物和中间体进行了结构表征;培养了中间体4,5-二氯肟基咪唑盐酸盐的单晶,用SHELXTL程序解析计算单晶的X射线衍射数据得到晶体的结构参数;利用DSC法分析了4,5-二氧代氰基咪唑盐酸盐的热分解性能。结果表明,4,5-二氯肟基咪唑盐酸盐晶体属于斜方晶系、Pna2(1)空间群,相对分子质量为259.47,密度为1.699g/cm3;4,5-二氧代氰基咪唑盐酸盐热分解温度始于140.23℃,经162.73℃和177.73℃两个分解放热峰,直至208.48℃分解放热结束,说明其结构比较稳定。     

[Mn（IMI）6]（ClO4）2的合成、晶体结构及感度

利用咪唑的水溶液和高氯酸锰水溶液反应制备高氯酸六咪唑合锰(II),培养出该配合物的单晶.用元素分析、红外光谱、DSC、TG-DTG和X射线单晶衍射等方法对该化合物进行了表征.结果表明,该晶体属于单斜晶系,空间群为P2(1)/n,晶胞参数a=11.721(2) nm, b=7.2191(13) nm, c=16.402(3) nm, β=90.064(3)°,V=1387.9(4) nm~3; Dc=1.585 g/cm~3; Z=2;F(000)=678, μ=0.160 mm, R_1=0.036 7, ωR2_=0.137 2.该化合物的分子式为[Mn(IMI)_6](ClO_4) _2,是由6个咪唑分子直接与二价锰离子配位、与高氯酸根离子结合形成的配合物.热分析结果表明,在10 K/min的升温速率下,该配合物的热分解过程由1个吸热峰和1个放热峰组成,剩余残渣量在9.9%左右.感度测试结果表明,该配合物为不敏感型的含能配合物.     

CL-20/FOX-7共晶的分子动力学模拟

依据共晶形成的氢键规则,搭建了7种CL-20/1,1-二氨基-2,2-二硝基乙烯(FOX-7)共晶模型;采用分子动力学(MD)模拟研究了CL-20/FOX-7共晶形成的可能性;通过径向分布函数(RDF)考察了共晶模型内分子的相互作用力;采用X-射线粉末衍射(XRD)模拟分析了共晶模型与纯组分间衍射峰的区别。结果表明,FOX-7和CL-20分子间存在较强的氢键和范德华力,7种共晶模型的结合能大小顺序为:Eb(1 0 1)Eb(1 1-1)E_b(随机晶面)E_b(0 1 1)E_b(0 0 2)E_b(1 1 0)E_b(1 0-1);7种共晶模型的分子间作用力以FOX-7取代CL-20(1 0 1)、(11-1)晶面较强;7种共晶模型的XRD衍射峰相较纯组分CL-20或FOX-7区别较大。据此推测在制备CL-20/FOX-7共晶过程中,FOX-7取代CL-20(1 0 1)晶面的共晶模型易于形成。     

含1,1–二氨基–2,2–二硝基乙烯推进剂的能量特性参数计算研究

利用国军标方法及CAD系统软件,在标准条件(pc∶p0=70∶1)下,计算了含1,1-二氨基-2,2-二硝基乙烯(FOX-7)的各类推进剂的能量特性参数,分析了氧化剂(AP、RDX、CL-20)及黏合剂(HTPB、PET、GAP、PBAMO)等成分对FOX-7推进剂能量特性的影响。结果表明,将AP加入HTPB/FOX-7推进剂配方中取代FOX-7可有效改善氧条件,有利于推进剂能量的提高。在黏合剂含量较低(质量分数<8%)的推进剂体系中,使用惰性黏合剂有利于提高推进剂的能量;而在黏合剂含量较高(质量分数>10%)的推进剂体系中,使用含能黏合剂提高推进剂能量的幅度优于惰性黏合剂,且GAP优于PBAMO。用FOX-7取代NEPE推进剂中的AP,推进剂最大理论比冲可达2 567 N.s/kg。由GAP/FOX-7/RDX组成的无烟推进剂,在很宽的范围内都可以达到2 400 N.s/kg以上的理论比冲值。     

配位聚合物[Cu(py)_2(m-bdc)]_n的合成、晶体结构及热分解动力学

采用溶剂扩散法合成了过渡金属配位聚合物:[Cu(py)2(m-bdc)]n(m-bdc=间苯二甲酸,py=吡啶),根据X-单晶衍射给出配合物的结构,该配合物是由间苯二甲酸根桥连的具有二维无限网状结构的聚合物,为单斜晶系,P 21/c空间群,晶胞参数:a=1.0017(5)nm,b=1.1358(6)nm,c=1.7014(7)nm,α=γ=90°,β=114.38(2)°,V=1.7631(15)nm3,Z=15,Dc=1.454 g·cm-3。应用非等温动力学研究技术研究了配合物的热分解机理,采用Ozawa法和KAS法给出了配合物热分解过程的活化能(Ea),用主曲线法得到了配合物热分解过程的机理函数积分式G(α)。结果表明:[Cu(py)2(m-bdc)]n在170℃开始分解,420℃分解结束。[Cu(py)2(m-bdc)]n的分解过程分两个阶段完成,两个分解阶段的表观活化能分别为72.971 kJ·mol-1,179.012 kJ·mol-1;机理函数的积分式分别为:G(α)=(-ln(1-α))0.48(1)、G(α)=(-ln(1-α))0.83(2)。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料，介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比，介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序，对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.