3-氟-4-硝基苯酚的合成研究

研究了以2,4-二氟硝基苯为原料,经甲氧基化、脱甲基化反应合成3-氟-4-硝基苯酚的新方法。探讨了反应条件对反应的影响：甲醇钠与2,4-二氟硝基苯物质的量比1：1,回流反应4h,得单氟代硝基苯甲醚;AlCl3与氟代硝基苯甲醚按物质的量比2．5：1在苯中回流反应10h,再经水蒸汽蒸馏分离提纯制得3-氟-4-硝基苯酚,质量分数99．5％,总收率38．7％。通过熔点测定、红外光谱和核磁共振等对产物结构进行了表征。     

9,9-二（4-羟乙氧基苯基）芴的合成工艺改进

9,9-二（4-羟乙氧基苯基）芴（BPEF）是合成聚酯聚醚重要的单体。采用9-芴酮和苯氧乙醇为原料,以浓硫酸作为催化剂,以少量巯基羧酸为助催剂,在原料配比（9-芴酮：苯氧乙醇：浓硫酸）=（1：4．5：1．5）,反应温度为50℃,反应时间为4h的反应条件下,得到目标产物。产品纯度〉99％,收率为95％（文献值为73．8％）,方法原料廉价易得,收率高,产品质量好,路线短。     

1-[3-（三氟甲基）苯基]-2-丙酮合成的研究

以间-溴三氟甲苯为原料,经格氏反应和氧化反应合成1-[3-（三氟甲基）苯基]-2-丙酮。反应优化条件为：溴化亚铜为催化剂,反应时间3h,反应温度5℃,氧化时n（重铬酸钠）：n（浓硫酸）=1：4。在此优化条件下。总收率82．3％。产物结构经IR和^1H NMR确证。     

一锅法合成2,4-二氟苯乙腈

研究了以2,4-二氟苯甲醛为起始原料,以水为溶剂经硼氢化钾还原,带水剂的作用下进行氯化和氰化反应一锅法合成2,4-二氟苯乙腈。考察了不同还原剂和带水剂对反应收率及产品质量的影响。结果表明,适宜的工艺条件为:2,4-二氟苯甲醛∶硼氢化钾∶氯化亚砜∶氰化钠=1∶0.36∶1.26∶1.35,用甲苯作为带水剂及氯化反应和氰化反应的溶剂,氰化反应的温度为90℃,反应时间3 h,总收率可达62.1%。该过程具有操作简单、适合工业化生产的特点。     

一锅法合成对苯撑二（4-氨基苯并恶唑）

用对苯二甲酸、2,4-二氨基苯酚盐酸盐为原料,五氧化二磷和磷酸反应生成的多聚磷酸为催化剂,合成了对苯撑二（4-氨基苯并恶唑）。考察了催化剂配比、原料配比及粗品精制溶剂等因素对产品纯度及收率的影响。结果表明,对苯二甲酸：2,4-二氨基苯酚盐酸盐=1：2．05;磷酸：五氧化二磷=1：1．35;采用混合溶剂进行精制,在此条件下产品的最终纯度达到99．2％     

4-氟苯甲醛的合成工艺研究

以4-氯苯甲醛（PCAD）和无水氟化钾为原料,采用卤素交换氟化反应,反应蒸馏技术一步合成4-氟苯甲醛（PFAD）。考察了溶剂、催化剂、投料比对反应的影响,得出最佳工艺条件为以1,3-二甲基丙撑脲为溶剂,四苯基二氟化氢膦盐（Ph4PHF2）为催化剂,n（KF）：n（PCAD）：n（Ph4PHF2）=3：1：0.1。在此条件下,反应与蒸馏同时进行,4-氟苯甲醛的收率可达90.6%。     

液相催化加氢制备2-氨基苯甲醇

以2-硝基苯甲醇为原料,乙酸乙酯为溶剂,负载型Ni为催化剂,采用液相催化加氢制备了2-氨基苯甲醇,考察了溶剂种类、温度、压力和催化剂用量对反应的影响。结果表明,该反应的最优化的工艺条件是：以乙酸乙酯为溶剂,反应温度50～60℃,反应压力1．5MPa,m（催化荆）／m（2-硝基苯甲醇）=1：10。在此条件下,产品收率可达...     

3,3-二甲基-1-丁烯合成条件的优化

探讨了合成3,3-二甲基-1-丁烯（新己烯）的最佳工艺条件。以叔丁醇和盐酸为原料,浓硫酸为催化剂合成氯代叔丁烷,探讨了反应温度和反应时间对收率的影响;采用加压方法,无水AlCl3为催化剂,以氯代叔丁烷和乙烯为原料合成氯代新己烷（2,2-二甲基丁烷）;确定了合适的加成反应条件,以N-甲基吡咯烷酮为溶剂,采用反应精馏的方法,氯代新己烷脱氯化氢制备新己烯。实验确定的最佳工艺条件：合成氯代叔丁烷的最佳反应温度为20℃,最佳反应时间为60 min;合成氯代新己烷的最佳反应压力为0.75 MPa,最佳反应温度为45℃;脱氯化氢制备新己烯的最佳溶剂为N-甲基吡咯烷酮。     

2-氟-5-溴硝基苯的合成

采用冰醋酸作为溶剂,以邻氟硝基苯为原料,N-溴代丁二酰亚胺(NBS)为溴代试剂,合成了2-氟-5-溴硝基苯。所得目标产物通过GC-MS定性、GC定量检测。结果表明,最佳反应条件为:n(邻氟硝基苯)∶n(NBS)=1∶1.05,以冰醋酸作溶剂,反应温度10℃,反应时间2 h,在该条件下2-氟-5-溴硝基苯的收率为98.6%,原料转化率100%。该反应条件温和,易于控制,重复性好。     

2，2-二溴-4，4，4-三氟乙酰乙酸乙酯的合成

以四氯化碳为溶剂,三氟乙酰乙酸乙酯和溴素为原料合成了2,2-二溴-4,4,4-三氟乙酰乙酸乙酯,研究了原料配比、反应温度、反应时间等因素对反应的影响,优化了最佳合成工艺条件：171（三氟乙酰乙酸乙酯）：n（溴素）=1：2．6,反应温度为25℃,反应时间20h,产物收率73．9％。产物结构通过。HNMrt和与IR进行了确证。     

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。