双稠合四硫富瓦烯衍生物的合成及电化学性质

以二硫化碳、二甲基甲酰胺等为起始原料,合成了3种新的非对称双稠合四硫富瓦烯(TTF)衍生物:2-(4′,5′-二烷硫基-1′,3′-二硫代环戊烯-2′-叉)-5-(4′,5′-二腈乙硫基-1′,3′-二硫代环戊烯-2′-叉)-1,3,4,6-四硫并环戊烯。通过元素分析、IR1、HNMR对产物结构进行了鉴定。系统地研究了这类非对称双稠合四硫富瓦烯衍生物的导电性能和电化学性质,结果表明除乙基和丙基取代的衍生物呈现半导体性质外,其他取代基的衍生物均为绝缘体。循环伏安研究显示所有化合物的电荷迁移分两步进行,但不是严格的电化学可逆。     

4-氰基戊酸二硫代苯甲酸合成新工艺研究

用铁氰化钾溶液氧化二硫代苯甲酸钠,得双二硫代苯甲酰,采用正交实验探讨了4,4’-偶氮双(4-氰基戊酸)与双二硫代苯甲酰反应的投料比、搅拌方式、反应时间对反应收率的影响。结果表明,4,4’-偶氮双(4-氰基戊酸)与双二硫代苯甲酰的最佳摩尔比为1.1∶1,在反应瓶中加入少许玻璃珠磁力搅拌,反应时间为16 h时,收率最高达到78%,两步总收率最高达到60%,远高于文献报道的44%。用IR和1H NMR表征了产物结构,证明获得所需的目的产物。     

一种改进的制备二硫代苯甲酸酯的方法及聚(N-异丙基丙烯酰胺)大分子链转移剂的制备

本研究采用改进的方法制备了二硫代苯甲酸(4-氰基戊酸)酯,反应以氯苄和氢氧化钠为原料制备二硫代苯甲酸(钠),反应产物经过用铁氰化钾氧化得到二硫代苯甲酸酐,最后与4,4'-偶氮4-氰基戊酸)反应就可以得到可逆加成-断裂链转移(RAFT)试剂二硫代苯甲酸(4-氰基戊酸)酯,此RAFT试剂与(N-异丙基丙烯酰胺)单体反应得到末端官能性聚(N-异丙基丙烯酰胺)大分子RAFT链转移剂.     

四硫富瓦烯基二硫纶及其配合物的合成

四硫富瓦烯-1,2-二硫纶(TTFDT)在有机金属导体领域有着良好的应用前景,通过恰当的分子设计可以开发出具有良好电导率的衍生物和配合物。设计、合成和表征了一种可作为配体前体的TTFDT衍生物,并且改进了其合成方法。     

4-异硫氰基-2-(三氟甲基)苯甲腈的合成

先以3-三氟甲基-4-溴苯胺(Ⅱ)为原料,与亚铁氰化钾发生氰基取代反应生成3-三氟甲基-4-氰基苯胺(Ⅲ);再以水为介质、DMF为有机溶剂,化合物Ⅲ与二硫化碳反应得到中间体3-三氟甲基-4-氰基苯基二硫代甲酸盐(Ⅳ);最后在三聚氯氰的作用下脱硫得到目标产物4-异硫氰基-2-(三氟甲基)苯甲腈(Ⅰ),反应总收率70.8%。目标产物的结构经1 HNMR和HPLC确证,HPLC纯度达99.5%。     

双稠合四硫富瓦烯衍生物的制备及取代基对合成的影响

扩展TTF衍生物的π共轭体系,可以增进分子导体中分子间的S…S相互作用,改善分子导电性。基于这个目的,以二硫化碳、二甲基甲酰胺为起始原料,合成了二种双稠合的四硫富瓦烯衍生物2．(4′,5′-二甲硫基-1′,3′,二硫代环戊烯-2′叉)-5-(4′,5′-二腈乙硫基．1′,3′-二硫代环戊烯-2′叉)-1,3,4,6-四硫并环戊烯和2,5-二(4′,5′-二甲硫基-1′,3′-二硫：、己环戊烯-2′-叉)-1,3,4,6-四硫并环戊烯。这两种化合物具有更为伸展的π共轭体系,因此有可能成为优良的电子给体。中间物及锄物经IR和元素分析进行了结构鉴定。同时讨论了取代基性质对双稠合四硫富瓦烯衍生物的合成收率的影响。     

二硫氰基甲烷中铁离子的测定-石墨炉原子吸收光谱分析

采用干灰化后石墨炉原子吸收光谱法测定了二硫氰基甲烷中铁离子的含量。将样品在不同温度下进行灰化至无黑色物,加入盐酸进行溶解,1%盐酸定容,然后采用石墨炉原子吸收光谱法测定铁离子的含量。在B建立的分析条件下,测定二硫氰基甲烷中的铁离子含量的方法具有较好的线性度、精密度和准确度,是较理想的分析方法。完全满足工业化对二硫氰基甲烷的质量控制。     

对杀菌剂二硫氰基甲烷分解的测定

二硫氰基甲烷是一种优异的非氧化性广谱杀菌灭藻剂,对各种真菌、藻类和细菌,包括好气菌和厌气菌都有良好的杀灭效果,广泛应用于工业循环水及油田注水处理中。它的分子结构式为SCN—CH_2—SCN。据研究,二硫氰基甲烷在水中会缓慢分解,产生新生态硫氰基。新生态硫氰基能通过与Fe~( )结合而阻断微生物呼吸过程中的电子转移,从而直接杀死微生物。     

四-(3,4-二甲氧基苯基)硫代双烯合镍的合成与光谱性能

以中间体二-(3,4-二甲氧基苯基)乙二酮为原料,经过P2S5硫化、镍络合,合成了四-(3,4-二甲氧基苯基)硫代双烯镍络合物近红外吸收染料.利用IR和1HNMR表征了最终产物硫代双烯合镍的结构.考察了四-(3,4-二甲氧基苯基)硫代双烯合镍在不同溶剂中的最大吸收波长及其光、热稳定性.     

共轭二茂铁衍生物的合成及晶体结构

在无溶剂条件下,以1,1-二氰基-2-二茂铁基丙烯和芳香醛为原料,肌氨酸为催化剂,通过微波辅助法合成D-π-A型共轭二茂铁衍生物(2-二茂铁基-1,1-二氰基-1,3-二烯衍生物)。利用核磁共振氢谱(1HNMR)、核磁共振碳谱(13CNMR)、红外光谱(FT-IR)等手段对化合物进行了表征。通过单晶X-射线衍射确定了化合物的晶体结构。晶体属于单斜晶系,P2(1)/c空间群。     

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。