环十二烷空气液相氧化制环十二烷醇(酮)的研究

研究了以偏硼酸为催化剂的环十二烷空气液相氧化制取环十二烷醇(酮)的工艺条件对氧化过程的转化率、选择性及收率的影响。提出了连续氧化操作更为合理的设想,并给出相应的工艺条件。     

环十二碳三烯连续加氢制环十二烷

探索了环十二碳三烯在滴流床中连续加氢制环十二烷的反应规律,采用ST-1催化剂,在压力2×10~6Pa、温度110C、液相空时83.4min、气液比大于3:1的条件下,环十二烷的收率可达99％以上,加氢产物可直接用于后续氧化反应。催化剂经近500h连续试验,活性和选择性均没有发生变化,可望应用于工业生产。     

环十二烷基胺的合成研究

环十二烷基胺（Ⅰ）可以由硝基环十二烷的还原［１，２］、或环十二碳烯在硫酸存在下与氢氰酸加成［３，４］或环十二酮（Ⅱ）的还原胺化法来制备。其中后者是为最简洁、合理的方法。前人曾报道Ⅱ与氨反应，催化氢化还原的方法获得较高收率的Ⅰ［５］：Ｏ（Ⅱ）＋ＮＨ３Ｈ...     

六溴环十二烷的研制

介绍了以环十二碳三烯溴化制六溴环十二烷的反应机理和简单易行的合成工艺,着重讨论了溶剂和催化剂对产品质量、收率的影响,经应用试验,获得较满意的阻燃效果。     

α-硝基环十二酮合成工艺的研究

以环十二烯为原料、NO2/O2为硝氧化试剂合成了α-硝基环十二酮。考察了温度、时间、溶剂、环十二烯浓度、脱硝试剂种类及用量等对反应的影响。结果表明经优化后的工艺条件,产品收率和纯度高,且反应周期短、条件温和、易于工业化生产。产品经1H NMR和13C NMR确证并通过高效液相色谱测定其含量。     

六溴环十二烷的合成研究

以环十二碳三烯(CDT)和溴素为原料,在乙醇、三氯甲烷混合溶剂中进行加成反应,合成六溴环十二烷阻燃剂。通过单因素实验,探讨了溶剂配比、滴加方式、反应物物质的量比、滴加时间等对六溴环十二烷各个异构体含量的影响,筛选出最佳的工艺条件为:m(乙醇):m(三氯甲烷)=1:1,滴加方式为溴素与CDT同时滴加,n(溴素):n(CDT)=3.5:1,滴加时间为8h,在该条件下收率为95%,γ异构体含量可达到80%。采用高效液相色谱对六溴环十二烷进行分析,检测α、β、γ各个异构体的含量,为最佳条件的选择提供依据。     

氯铝酸盐离子液体催化苯与十二烯烷基化反应

针对酸性氯铝酸盐室温离子液体[BMIM][AlCl4]催化苯与1-十二烯烷基化合成十二烷基苯反应体系的物理化学特性,设计了一套可以分别进行间歇和连续操作的连续流动搅拌反应装置。间歇操作的反应结果表明．[BMIM][AlCl4]催化剂体系的总体结果优于传统催化剂无水AlCl3和氢氟酸,催化剂的用量和反应温度可以大大降低,2-苯基异构体的选择性较高。在连续操作条件下,一定的流量范围内实现了离子液体催化剂和反应料液的原位分离,催化剂被有效地局限在反应区域,并因在运转过程中始终未暴露从而得到了比间歇操作更加稳定和高效的反应结果。     

环十二酮在香料合成中的应用研究

综述了环十二酮在香料合成中的应用。环十二酮在大环化合物尤其是麝香酮的合成中发挥着非常重要的作用,并比较了几种合成方法的工业化前景。环十二酮在环十五内酯和其他物质的合成中也得到了广泛的应用。     

十二烷基三甲氧基硅烷的合成

以三氯氢硅、1-十二碳烯为原料,在铂催化剂存在下合成出十二烷基三氯硅烷;并以溶剂法醇解得到十二烷基三甲氧基硅烷。考察了催化剂用量、原料配比、反应时间对加成反应的影响,溶剂、原料配比、温度等因素对醇解反应的影响。最佳反应条件为:在加成反应中,当铂催化剂与三氯氢硅的量之比为3.6×10-4∶1、三氯氢硅与1-十二碳烯的量之比为1.15∶1时,十二烷基三氯硅烷的收率达81%,反应在室温下无诱导期即可发生、且无需改变加料方式、反应时间短、副反应少、收率高;醇解反应采用溶剂法,将十二烷基三氯硅烷滴加到甲醇中,十二烷基三氯硅烷与甲醇的量之比为1∶3.2,底温控制在70℃,N2流量为80 mL/min,十二烷基三氯硅烷的滴加速度为1 mL/min,十二烷基三甲氧基硅烷的收率为85%。     

锌、铝氧化物催化合成十二烷二腈

以氧化锌与氧化铝混合物为催化剂,十二烷二酸为原料制备十二烷二腈,探讨了催化剂对十二烷二腈制备工艺的影响。结果表明,以原料质量6%的氧化锌和3%的氧化铝混合催化剂催化效果最好;实验过程中,釜内氨气压0.4 MPa,升温至200℃开启搅拌(200 r/min),最高反应温度280℃。在此条件下,产率为82%,产品质量分数91%。产物经红外光谱和气质色谱确认。经适当改进后可实现工业化生产。     

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。