TADBIW在丙酸和正丁酸中的氢解脱苄

四乙酰基二苄基六氮杂异伍兹烷(TADBIW)是六苄基六氮杂异伍兹烷(HBIW)的氢解脱苄产物。在不同．酸性体系中氢解TADBIW将得到不同的脱苄产物。以丙酸和正丁酸为氢解介质,采用自制的Pd系催化剂氢解TADBIW制得了四乙酰基六氮杂异伍兹烷(TAIW),并对其反应过程做了初步的探讨。     

四乙酰基二亚硝基六氮杂异伍兹烷的合成与表征

采用无机亚硝解试剂由六苄基六氮杂异伍兹烷(HBIW)的一次氢解产物四乙酰基二苄基六氮杂异伍兹烷(TADBIW)合成四乙酰基二亚硝基六氮杂异伍兹烷(TADNSIW),维持温度25℃,反应1h,TADNSIW得率为81 0%。对产物进行了分离、提纯,目标产物熔点为288～290℃。并用FT-IR、1HNMR、MS及元素分析法对目标产物进行了结构鉴定。定量地分离出副产物苯甲醛,并由此证明该文所提反应机理的合理性。     

制备六硝基六氮杂异伍兹烷的硝解工艺近期进展

六硝基六氮杂异伍兹烷(HN研)是当今已工业化生产的能量水平最高的炸药，HNIW的制备包括基本母体的合成、母体的氢解、氢解产物(硝解底物)的硝解(即生成HN研)及HNIW的转晶4步。综述了近几年来制备HNIW的硝解工艺的进展(包括作者的若干研究成果)，详细报道了硝解3种底物([四乙酰基二苄基六氮杂异伍兹烷(TADBIW)、四乙酰基二甲酰基六氮杂杂异伍兹烷(TADFIW)及四乙酰基六氮杂异伍兹烷(TAIW]）以制备HNIW的工艺条件，并评价了各自的优、缺点。     

六氮杂异伍兹烷衍生物的氧化反应

研究了以过硫酸铵作为氧化剂，乙酸酐作为反应介质，在硝酸饰铵(Ⅳ)催化下四乙酞基二苄基六氮杂异伍兹烷的氧化脱苄反应，并将这种方法应用到六苄基六氮杂异伍兹烷的脱苄上，成功地通过氧化法合成出四乙酞基二苄基六氮杂异伍兹烷。     

由四乙酰基二苄基六氮杂异伍兹烷合成六硝基六氮杂异伍兹烷

以四乙酰基二苄基六氮杂异伍兹烷为基质,经亚硝解脱苄合成了四乙酰基二亚硝基六氮杂异伍兹烷(TADNSIW);用纯硝酸氧化TADNSIW制备四乙酰基二硝基六氮杂异伍兹烷(TADNIW),收率93.0%,以上两步反应均在室温下完成。在85℃条件下,TADNIW经硝硫混酸硝解合成了六硝基六氮杂异伍兹烷(HNIW),反应时间50 m in,收率95.1%,质量分数98.80%。用硝硫混酸对TADNSIW进行硝解合成了HNIW,并优化了反应条件,反应温度90℃,反应时间60 m in,硝解剂必须大于14 mL(底物TADNSIW 1.2 g),收率为96.1%,质量分数98.87%。分别用FTIR,1HNMR和元素分析对目标化合物进行了表征。前体TADNSIW和TADNIW分子中只有乙酰基和亚硝基,它们的硝解反应体系较简单,反应时间短、反应条件温和,母液中只含有乙酸和硝解剂,产物易分离。     

不同载体钯催化剂的结构表征及其在笼形叔胺脱N-苄基上的应用

以γ Al2O3、木质活性炭、煤质活性炭为载体,以氯化钯为前体制备了Pd(OH)2/Al2O3、Pd(OH)2/C催化剂,并用X射线衍射、透射电镜和X射线光电子能谱等技术对这些催化剂进行了结构表征。以六苄基六氮杂异伍兹烷(HBIW)的脱苄反应为例,研究了不同载体Pd(OH)2催化剂对笼形叔胺N 苄基脱苄反应的活性,分析了影响催化剂活性的各种因素。实验结果表明,当催化剂用量为HBIW质量的0 2%(以Pd计)时,氢解产品四乙酰基二苄基六氮杂异伍兹烷(TADBIW)的收率可达88%,其中以煤质活性炭为载体的催化剂已用于HBIW氢解脱苄的20kg级放大实验,TADBIW产品收率为82%。     

六苄基六氮杂异伍兹烷氧化产物的亚硝化

采用硝酸（65％）／亚硝酸钠体系对六苄基六氮杂异伍兹烷氧化物－乙酰基三苯甲酰基二苄基六氮杂异伍兹烷（3）、二乙酰基二苯甲酰基二苄基六氮杂异伍兹烷（4）和三乙酰基一苯甲酰基二苄基六氮杂异伍兹烷（5）进行亚硝解，成功脱去了上述三种化合物上剩余的两个苄基，将苄基转换为亚硝基，得到了一乙酰基三苯甲酰基二亚硝基六氮杂异伍兹烷（6）、二乙酰基二苯甲基二亚硝基六氮杂异伍兹烷（7）和三乙基酰基一苯甲酰基二亚硝基六氮杂异伍兹烷（8）。     

六苄基六氮杂异伍兹烷氧化产物的亚硝解反应

采用65％硝酸／亚硝酸钠体系对六苄基六氮杂异伍兹烷氧化产物四苯甲酰基二苄基六氮杂异伍兹烷(1)和五苯甲酰基-苄基六氮杂异伍兹烷(2)进行亚硝解，脱去了剩余的苄基，将苄基转换为亚硝基，得到了四苯甲酰基二亚硝基六氮杂异伍兹烷(3)和五苯甲酰基-亚硝基六氮杂异伍兹烷(4)。     

TADB氢解脱苄合成TADF的反应动力学

采用Pd(OH)2/C催化剂,研究了常压下四乙酰基二苄基六氮杂异伍兹烷(TADB)在甲酸介质中氢解脱苄合成四乙酰基二甲酰基六氮杂异伍兹烷(TADF)的反应动力学。通过空白实验消除催化剂及溶剂对吸氢量的影响,以吸氢量来表征反应程度。通过积分反应速率方程,对不同温度下该反应的实验数据进行了动力学计算。实验结果表明,在实验条件下,TADB的氢解脱苄对于TADB是一级反应,反应表观活化能为50.41kJ/mol,指前因子为4.5326×106min-1。而用Pd/C催化剂时,该溶液放出氢气且反应不完全。     

钯催化TADBIW氢解合成TAIW

利用沉淀-还原法合成了一系列的钯基双金属催化剂,催化四乙酰基二苄基六氮杂异伍兹烷(TADBIW)氢解合成四乙酰基六氮杂异伍兹烷(TAIW)。探究了以SiO₂、Al₂O₃、TiO₂为载体,Fe、Co、Ni等金属助剂和催化剂用量对产物TAIW收率的影响。结果表明,在50℃、0.5 MPa H₂,以10%Pd-Ni/TiO₂为催化剂,催化剂用量为4%,催化TADBIW氢解反应,产物TAIW收率达91%。采用XRD、XPS、ICP、TEM等手段表征了Pd-Ni/TiO₂催化剂的结构和形貌。将产物TAIW进一步硝化合成CL-20,产物CL-20收率达90%。     

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.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

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。