近临界水中苯甲醛稳定性的研究

测定了压力15MPa,温度260-310℃下苯甲醛在近临界水中的稳定性数据。由Arrhenius方程拟合得到苯甲醛分解反应的表观活化能为51．65kJ／mol。利用气相色谱-质谱（GC／MS）对分解产物进行了定性分析,表明分解产物中除了苯甲醇和苯甲酸外,还有大分子物质,进而探讨了苯甲醛在近临界水中的分解机理。     

近临界水中乙酰丙酸的稳定性

乙酰丙酸有望成为一个基于生物质资源的新平台化合物,其制备过程中涉及高温高压水.实验测定了压力10 MPa、温度220～280 ℃内乙酰丙酸在近临界水中的稳定性.实验结果表明:近临界水中乙酰丙酸较稳定,在280 ℃、反应32 h下,乙酰丙酸的转化率仅为7.0%.乙酰丙酸降解反应为一级反应,分解反应的活化能为28.04 kJ/mol.     

不同植物油脂在近临界水中水解反应动力学的比较

系统地测定了压力10 MPa、温度170℃～240℃范围内橄榄油、花生油、大豆油、红花油等植物油脂在近临界水中无催化水解反应动力学数据。实验结果表明,近临界水中油脂水解反应是一个典型的自催化反应,采用二级自催化反应动力学模型对动力学数据进行了拟合,得到了橄榄油、花生油、大豆油、红花油等四种植物油脂的水解反应活化能分别为41.8 kJ/mol、37.3 kJ/mol、37.7 kJ/mol、31.2 kJ/mol。油脂水解活化能与其碘价密切相关,随着油脂碘价的增加,水解活化能逐渐降低。     

肉桂醛绿色合成新方法

提出了一种以水为反应介质合成肉桂醛的新方法.在近临界水中,以苯甲醛和乙醛为原料,在无外加任何催化剂的条件下,合成肉桂醛.在温度220～300 ℃范围内,测定了温度和反应时间对苯甲醛转化率和肉桂醛收率的影响.对反应条件进行了优化,在反应温度260 ℃,压力16 MPa,反应物和水体积比1∶15,反应时间5 h条件下,肉桂醛产率可达16.6%.     

氢气在煤液化油中溶解度的测定

建立了一套测定高温高压下气体溶解度的实验装置,经检验准确可靠．利用此装置和平衡液相取样法,在25rC～350℃,2MPa～10MPa的温度和氢气压力范围内,测定了氢气在煤液化低温分离器油中的溶解度．结果发现,在实验测定范围内,氢气在低温分离器油中的溶解度分别随温度和氢气压力的升高而几乎都呈线性增大,温度350℃,氢气压力9．515MPa时达到最大值0．3381mol／kg;氢气溶解度和其压力关系并不严格遵守亨利定律．     

近临界水中苯甲醛合成新方法

测定了压力15 MPa下,温度240～320℃范围内肉桂醛水解反应的动力学数据.实验结果表明在无任何外加催化剂的情况下,肉桂醛能够在近临界水中顺利进行水解反应生成苯甲醛,苯甲醛产率随时间的延长先增大后减小.随温度升高,水解反应速率迅速增大,苯甲醛产率达到最大值的时间缩短.得到较佳反应条件为15 MPa、280℃、反应时间6h,此时苯甲醛产率为57.0%(mol).由Arrhenius方程,拟合得到肉桂醛水解反应的活化能为59.8 kJ·mol-1.本方法制备的苯甲醛由于没有引入其它反应物,因此香气品质较佳.     

Mn2+催化超临界水氧化偏二甲肼

采用Mn2 为催化剂、H2O2为氧化剂,在24~30 MPa和400~500℃的条件下,在一连续流反应器中进行了催化超临界水氧化偏二甲肼实验。研究了温度、压力、停留时间和Mn2 浓度对偏二甲肼氧化降解的影响。结果表明,在超临界水中偏二甲肼能被有效去除。偏二甲肼的去除率随反应温度和压力的升高、停留时间的延长和Mn2 浓度增大而提高。当Mn2 浓度为30 mg/L时,偏二甲肼的去除率与无催化剂时相比有了较大的提高。当30 MPa、500℃、3.6 s和Mn2 浓度为30 mg/L时,COD去除率高达99.6%。     

亚临界水中橡胶籽油水解反应的试验研究

探讨油脂在亚临界水中水解反应的影响因素和反应动力学。以橡胶籽油为原料,在间歇式高温高压反应釜中进行水解反应,试验结果表明,在水与橡胶籽油体积比为3∶1(摩尔比为162∶1),反应温度280℃,压力15 MPa,反应时间40 m in时,橡胶籽油水解为脂肪酸的转化率可达96.2%;动力学计算表明,橡胶籽油在亚临界水中水解反应级数为1.4,反应活化能为43.5 kJ/mol。该研究为超临界二步法制备生物柴油的水解反应的动力学提供了理论基础。     

近临界水中薯蓣皂苷的水解反应

在近临界水中研究了薯蓣皂苷水解成薯蓣皂苷元的工艺和反应动力学,分别考察了反应温度、压力、时间等因素对薯蓣皂苷元收率的影响。实验结果表明,近临界水解法的较佳工艺条件为260℃,25 MPa,反应10 min。在此条件下,薯蓣皂苷元收率为1.46%。动力学研究结果表明,薯蓣皂苷在近临界水中水解是一级反应,活化能为76.7 kJ/mol,指前因子k0为5.99×104s-1。     

正己烷、正辛烷在临界二氧化碳中的相平衡

<正> 本文应用一种新型的汽液双循环高压平衡釜测定了正己烷和正辛烷分别在临界二氧化碳中的相平衡数据。测定范围压力为(18～87)×1.0133×10~5Pa,温度为30～60℃。实验流程如图所示。     

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。