正丁基硫代磷酰三胺的合成工艺改进

以三氯硫磷和正丁胺为原料,采用管式反应器制得中间体正丁基硫代二磷酰氯,然后室温通氨气反应3 h制得正丁基硫代磷酰三胺,总收率达65.1%。目标化合物经IR、ESI-MS、1HNMR和13CNMR表征确认,考察了原料配比、反应温度、停留时间对反应总收率的影响,优化的合成工艺参数为:投料配比n(三氯硫磷)∶n(正丁胺)=1∶1.5,停留时间为30 s,管长14 m,管径3 mm,反应温度28～30℃。     

“一锅法”合成14-O-[(2-氨基-1, 1-二甲基乙基)硫甲羰基]目特林

以截短侧耳素、对甲苯磺酰氯和二甲基半胱胺盐酸盐为主要原料,以乙醚为溶剂,采用一锅法合成沃尼妙林中间体14-O-[(2-氨基-1,1-二甲基乙基)硫甲羰基]目特林。最佳工艺条件为:n(截短侧耳素)∶n(对甲苯磺酰氯)∶n(二甲基半胱胺盐酸盐)=1∶1.1∶1.1;相转移催化剂为四丁基溴化铵,用量为1.6 g;反应温度为30℃;反应时间为2.5 h;目标产物收率达91%。并用正交设计法对主要工艺条件进行了优化,结果与单因素实验结果相同。产品结构通过核磁共振波谱、红外光谱进行了表征,测定了产物的熔点。     

N,N′-双(对甲苯磺酰基)-2-哌嗪羧酸甲酯的合成

由乙二胺和对甲苯磺酰氯反应制得N,N′-双(对甲苯磺酰基)乙二胺。此步最佳工艺条件为:n(对甲苯磺酰氯)∶n(乙二胺)=2.2∶1,反应溶剂为苯,反应温度为40～45℃,反应时间为6h,收率80%。由丙烯酸甲酯和溴反应制得α,β-二溴丙酸甲酯,收率为88%。再由上述二种中间体反应合成标题化合物,此步省略了N,N′-双(对甲苯磺酰基)乙二胺的二钠盐制备,收率为73%。     

螯合剂聚乙烯亚胺二硫代氨基甲酸盐双催化绿色合成的方法研究

针对螯合剂聚乙烯亚胺二硫代氨基甲酸盐合成中反应时间长、收率低、反应不充分等不足,选用4-二甲氨基吡啶、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐双催化剂,聚乙烯亚胺、氢氧化钠水溶液、二硫化碳为原料,优化反应条件,形成一种聚乙烯亚胺二硫代氨基甲酸盐双催化的绿色合成方法。     

2-萘二硫醚制备新工艺研究

以2-萘磺酰氯为原料,以碘化钾/亚硫酸氢钠/甲酸组成的还原体系制备标题化合物,产物的结构经~1HNMR和~(13)CNMR表征。通过单因素和正交试验,考察反应物物质的量比、反应温度、反应时间等对收率的影响,最终确定合成标题化合物的最优条件为:n(2-萘磺酰氯)∶n(亚硫酸氢钠)=1∶4、n(2-萘磺酰氯)∶n(甲酸)=1∶3. 5、n(2-萘磺酰氯)∶n(碘化钾)=1∶2. 5、水作为溶剂、反应温度为100℃、反应时间2. 5 h,产品收率为69. 7%,纯度可达96%以上。该方法原料易得、操作简单,并实现了对还原剂的部分循环利用,为工业化奠定了基础。     

稀土配合物二硫代氨基甲酸盐类的合成及其性能研究

本文探讨了稀土配合物二硫代氨基甲酸盐类合成条件,并确定配体二苄基二硫代氨基甲酸钠(NaDBTC)反应的最佳条件为:n二苄胺∶nNaOH∶nCS2=1.0∶1.5∶1.8;反应时间在2h。最后,合成了该配体与稀土的配合物。     

金刚烷胺季铵盐的合成

通过比较三种N-甲基化方法,确定用甲醛-甲酸体系的还原烃化法制成N,N-二甲基-1-金刚烷胺,优化条件为金刚烷胺∶甲醛∶甲酸的摩尔比为1∶3∶3,反应时间为18 h,温度为100℃,收率为91.5%。然后分别与碘甲烷、溴甲烷及硫酸二甲酯反应,合成了三种N,N,N-三甲基-1-金刚烷基季铵盐。目标化合物结构经1H NMR和MS验证。     

2-羟基-4-(N-乙基-N-异丁基)氨基-2’-羧基二苯酮的合成工艺

目前有关荧烷染料中间体的合成方法国内少有报道。2-羟基-4-(N-乙基-N-异丁基)氨基-2’-羧基二苯酮是一种重要的荧烷类压热敏染料中间体,本文以N-乙基-N-异丁基间氨基苯酚为原料与邻苯二甲酸酐在氮气保护下反应合成,并在反应后使用NaOH溶液分解副产物,以提高产物纯度,通过HPCE测定产物纯度达到96.36%(面积归一法)。使用TLC对反应进程进行监测,并通过UV对TLC检测结果进行确认,详细讨论了物料比、温度和时间等条件对反应的影响,并得出二苯酮合成反应中N-乙基-N-异丁基间氨基苯酚与邻苯二甲酸酐摩尔比为1∶1.5,温度为110℃,时间为15h时反应效果最佳。副产物若丹明染料分解反应中NaOH溶液浓度为33.3%,N-乙基-N-异丁基间氨基苯酚与NaOH的质量比为1∶7.5,温度为90℃,时间为9h时反应效果最佳。最后通过IR和UV对目标产物结构进行确认。     

一种N-二甲氧基乙基-间氨基乙酰苯胺的合成工艺

正本发明公开了一种N-二甲氧基乙基-间氨基乙酰苯胺的合成工艺,以乙二醇单甲醚和氯化亚砜进行氯化反应制得氯乙醇单甲醚,然后加入间氨基乙酰氨基苯胺盐酸盐、纯碱和四丁基溴化铵进行双取代反应制得目标产品。本发明将传统工艺中相对价格较高的对甲苯磺酰氯替换成氯化亚砜,降低了成本;本发明的反应条     

亚乙基双二硫代氨基甲酸二钠合成的研究

在30~40℃水溶液中,乙二胺与二硫化碳反应,制备出二硫代氨基甲酸中间体即亚乙基双二硫代氨基甲酸,然后与48%氢氧化钠溶液反应,制备出亚乙基双二硫代氨基甲酸二钠水溶液,该水溶液是一种农药杀菌剂。     

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。