β-异佛尔酮催化氧化制酮代异佛尔酮

研究了以 β-异佛尔酮为原料 ,在催化剂存在下 ,用分子氧氧化制备酮代异佛尔酮的合成工艺。考察了催化剂用量、反应温度、反应时间、通氧速率、搅拌速度等因素对酮代异佛尔酮产率的影响。在较佳的实验条件下 ,酮代异佛尔酮的收率达 94%以上     

异佛尔酮合成工艺的研究进展

介绍了异佛尔酮合成工艺的发展历程,重点介绍了丙酮液相缩合法和气-固多相催化缩合法制备异佛尔酮的生产现状及近年来的研究进展,同时对已有和在研的工艺方法进行了分析、比较,指出了各种工艺的优缺点,并展望了国内异佛尔酮生产IPDI的应用前景。     

异佛尔酮工业生产的模拟试验

异佛尔酮是一种优良的高沸点溶剂，广泛用于轿车烘漆、食品罐头内壁涂层等方面，目前我国尚无厂家生产。本文介绍采用丙酮在固体碱催化剂床层上进行气、固催化缩合反应制取异佛尔酮馏份的试验过程和结果，提出了获得较高异佛尔酮馏份收率的工艺条件，并对催化剂的再生工艺作了介绍。方法简便、原料与动力消耗低，适于实现工业化。     

Degussa扩大异佛尔酮生产规模

随着在德国Herne地区异佛尔酮正式生产线的建立，Degussa集团开始了异佛尔酮扩能和发展的路程。由于Degussa生产能力进一步增长，日益巩固了其在市场上的领先地位。加上目前在Herne地区3条异佛尔酮生产线，Degussa集团目前共拥有4条生产线。异佛尔酮化学试剂可被用在汽车涂料、工业地板中，也可用于防腐项目。     

异佛尔酮二胺的合成及工艺优化

以异佛尔酮为原料,经氰化、亚胺化和氢化三步反应合成了异佛尔酮二胺,并对反应工艺条件进行了优化。中间产物异佛尔酮腈合成的优化实验条件:NH4Cl为酸化试剂、DMF为反应介质、0.0669 mol异佛尔酮和0.048 mol Na CN与5 m L浓度为6 mol·L-1的NH4Cl水溶液在70℃下反应4 h,得异佛尔酮腈,收率为94.9%。中间产物异佛尔酮亚胺合成的优化实验条件为:以Ca O为催化剂、氨压0.2 MPa、70℃反应4 h,异佛尔酮腈转化率为97.4%,异佛尔酮亚胺收率为87.6%。异佛尔酮二胺合成的优化实验条件为:温度120℃、氢压6 MPa、氨压0.2 MPa、催化剂为2.0 g Raney Co,反应8 h后,异佛尔酮亚胺的转化率为100%,异佛尔酮二胺的收率为95.6%。另外,对中间产物和终产物分别进行了IR、MS、1H-NMR等分析,确认其结构无误。     

丙酮缩合制异佛尔酮研究进展

近年来我国丙酮产量持续增长,丙酮产能逐渐过剩,与此同时,丙酮的高附加值利用相对较少;丙酮缩合制异佛尔酮,随后生产异佛尔酮二胺、异佛尔酮异氰酸酯等能够大大提高丙酮利用的附加值.本文对目前丙酮缩合制异佛尔酮的生产路线及催化剂研究进展进行了总结,重点介绍了有工业化应用的代表性工艺及催化剂,如以碱性氢氧化物为催化剂的丙酮液相缩合法以及以镁铝水滑石为催化剂的气相缩合法;在此基础上,进一步介绍了镁铝固体碱催化剂催化效果的影响因素,并对现有异佛尔酮合成工艺方法进行了分析、比较.最后对异佛尔酮的发展前景进行了展望.     

不饱和酮—异佛尔酮的制备

异佛尔酮不仅是一种重要的不饱和酮类溶剂,它在精细化工中有着极为广泛的用途。本文介绍了一种适宜于在实验室内及小规模生产异佛尔酮的方法。具有设备投资少、工艺简单及可在较短时间内投产的特点。使用本方法,丙酮的单程转化率为50％,异佛尔酮的产率为20％。     

氧化异佛尔酮（3,5,5—三甲基环乙烯—1,4—二酮）的合成研究

用乙酰乙酸乙酯和异丙叉丙酮为原料合成了α－异佛尔酮，再用格氏试地将α－异佛尔酮转位成β－异佛尔酮。然后在特殊的Ｍｎ＃或Ｃｏ＃携氧螯合催化剂作用下，再将其氧化异佛尔酮。盲人经剂氧化效果良好，产率可达到６３％，用格多试剂法合成β－异佛尔酮比用乙二醇合成转化更彻底，产率可达７０％。     

异佛尔酮二异氰酸酯的三聚研究

研究了季铵盐等催化剂对异佛尔酮二异氰酸酯(IPDI)三聚反应的催化效率,探讨了季铵盐用量、反应温度、反应时间等工艺参数的影响,结果表明,季铵盐具有较好的催化活性;当季铵盐催化剂质量分数为0.25%左右,反应温度为60℃,反应时间为2.0~2.5h时,异佛尔酮二异氰酸酯三聚反应工艺条件最佳,得到的产品色浅,三聚体含量高,并用红外光谱和凝胶渗透色谱对产物进行了表征。     

氧代异佛尔酮的合成

氧代异佛尔酮（KIP）是合成维生素E的重要中间体,目前主要有两条合成路线。本文研究了以α-异佛尔酮为原料,在催化体系作用下,用分子氧氧化制备氧代异佛尔酮的合成工艺。同时采用喷射氧化反应,验证了催化剂用量、反应温度、氧含量等因素对收率的影响。     

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。