阻燃剂磷酸双(2,3-二溴丙基)二氯丙酯的合成

研究了以三氯氧磷、环氧氯丙烷和2,3-二溴丙醇为原料,应用复合催化剂和在通氨气的条件下合成磷卤协效阻燃剂——磷酸双(2,3-二溴丙基)二氯丙酯的新方法。探讨了反应时间、反应温度和催化剂及溶剂等对产品收率的影响,筛选出最佳的反应条件,产品收率达80%以上。     

一种含磷-氮-溴膨胀型阻燃剂的合成

以苯酚、溴素、双氧水、三氯氧磷、三聚氰胺等为原料,经三步合成含磷-氮-溴膨胀型阻燃剂双-(2,4,6-三溴苯基)磷酸二酯二三聚氰胺盐。第一步以乙醇为溶剂,苯酚、溴素与双氧水的摩尔比为1∶1.55∶1.78时,中间体Ⅰ三溴苯酚的收率达到98.2%;第二步以苯为溶剂、吡啶为缚酸剂,中间体Ⅰ与三氯氧磷的摩尔比为2.3∶1时,中间体Ⅱ的收率达到89.1%;第三步以DMSO为溶剂,反应温度为130℃,目标产物Ⅲ的收率达到95.8%。采用红外光谱和质谱对中间体及目标产物进行了结构表征。     

1-溴-2-甲基萘的合成研究

以2-甲基萘为原料,在甲醇为溶剂的条件下,以双氧水-氢溴酸为溴化剂,制备出了高纯度的1-溴-2-甲基萘,考察了反应条件对产品收率影响。优化反应条件为:n(2-甲基萘):n(氢溴酸):n(双氧水)=1:1.6:1.6,反应温度控制在0~5℃,此条件下产品收率达到94%,产品结构经过MS和1HNMR确认。     

1-甲氧基-2-甲基萘的合成研究

以2-甲基萘为原料,在惰性的卤代烃溶剂中低温下进行溴化反应,制备1-溴-2-甲基萘;溴化产物在碘化亚铜催化下,和甲醇钠进行烷氧基化反应制得1-甲氧基-2-甲基蔡。产品纯度〉99％（GC）,总收率87．4％．产品结构经MS和^1H NMR确认。考察了反应条件对产品收率和纯度的影响。     

关于合成2-溴-2-硝基-1,3-丙二醇新方法的研究

通过硝基甲烷先溴化再缩合的方法合成了2-溴-2-硝基-1,3-丙二醇,合成最佳反应条件为：在溴化反应中,NaOH与CH3NO2的物质的量比为1．1：1．0,NaOH溶液的质量浓度为25％,成盐温度为-5～0℃,溴化温度为15℃;在缩合反应中．溶液pH5～6,缩合温度为25℃,V镕剂：V反应原料=2．0：1．0。质量分数为98％,产品总收率为83．5%。     

2-溴-4-氨基苯甲醚的合成

以4-硝基氟苯为原料,经芳环溴代、亲核取代、硝基还原,共3步反应制得2-溴-4-氨基苯甲醚。考察了反应物用量、反应温度和反应时间对溴酸钠溴代法收率的影响,考察了3种还原法对还原收率的影响。当n(4-硝基氟苯)∶n(硫酸钾)=50∶1,反应温度为68℃,反应时间为3h时,溴代反应收率为69.6%;以10%Pd-C/甲酸铵还原硝基时,反应收率为92.3%;3步反应的总收率为61.0%。各步产物结构均经MS、1 H NMR进行表征。     

2-溴-3-甲基-1,4-二甲氧基萘的合成

以2-甲基萘醌为原料,经过催化氢化、甲醚化和溴化3步反应,合成了维生素K2的重要中间体2-溴-3-甲基-1,4-二甲氧基萘(1)。以钯碳为催化剂加氢还原,得到了2-甲基-1,4-二羟基萘(3),收率98.8%;3在碱性条件下用硫酸二甲酯进行甲氧基保护,生成2-甲基-1,4-二甲氧基萘(4),收率95.1%;4与溴反应可以得到1,收率90.1%。3步反应总收率由传统方法的48.7%提高到84.6%。     

2-溴-3-甲基-1,4-二甲氧基萘的合成新方法研究

以2-甲基萘醌(2)为原料,经过催化氢化、甲醚化和溴代三步反应,合成了维生素K2的重要中间体2-溴-3-甲基-1,4-二甲氧基萘(1)。(2)催化加氢还原得到2-甲基-1,4-二羟基萘(3)。(3与硫酸二甲酯反应生成2-甲基-1,4-二甲氧基萘(4),甲醚化反应通过正交实验可使产物收率达到95.1%;(4)与溴反应,经单因素实验在较佳的反应工艺条件下得到目标产物(1),收率90.1%。三步反应总收率达到84.6%。     

5-溴-2-氰基吡啶的新合成方法研究

以2-氨基-5-溴吡啶为起始原料,采用三氯氧磷/二氯甲烷/吡啶(POCl3/CH2Cl2/Pyridine)体系为脱水试剂,经3步反应合成5-溴-2-氰基吡啶。     

2-(2-溴乙酰基)-2-乙基茚酮的合成

以氢化肉桂酸(3-苯基丙酸)为起始原料,经过环合、乙酰基化、乙基烷基化以及溴化4步反应合成了2-(2-溴乙酰基)-2-乙基茚酮,总收率54.7%。通过MS和1H NMR对目标产物及各步反应中间体的结构进行了表征。对不同的乙酰基化方法进行了对比研究后,采用傅克酰基化的方法并采用正交实验法优化了反应条件,确定了最优反应条件:反应时间6 h,反应温度10℃,n(三氯化铝)∶n(1-茚酮)=2∶1。考察了乙基烷基化和溴化过程中不同温度对收率的影响,确定了最佳反应温度。     

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。