N-甲基吡咯烷酮硫酸氢盐催化合成乙酸环己酯

以新型离子液体N-甲基吡咯烷酮硫酸氢盐([Hnmp]HSO4)为催化剂,环己烷为带水剂,对乙酸环己酯的酯化反应进行了研究,重点考察了催化剂用量、反应温度、反应时间、酸醇摩尔比和带水剂等因素对乙酸环己酯产率的影响。实验结果表明,[Hnmp]HSO4对合成乙酸环己酯有着良好的催化活性,当催化剂用量为环己醇物质的量的1%,乙酸和环己醇的摩尔比为1.4∶1,环己烷为10 mL,油浴温度125℃反应2 h后,乙酸环己酯产率可达90%以上,且催化剂重复使用6次仍保持较高活性。腐蚀性实验表明,[Hnmp]HSO4对不锈钢的腐蚀率为0.015 2 g·m-2·h-1。     

酸性离子液体催化合成乙酸苯乙酯

以酸性离子液体己基甲基咪唑硫酸氢盐[n-C6Im][HSO4]为催化剂催化合成乙酸苯乙酯(PEAC)。通过对影响转化率的各种因素考察,得到最佳合成条件:2-苯乙醇与乙酸乙烯酯物质的量比为1∶1.2,离子液体催化剂用量5%(质量分数),反应温度140℃,反应时间6 h,PEAC转化率为91.8%。离子液体催化剂重复使用4次后,转化率开始缓慢下降,但补充适量硫酸后离子液体即可恢复催化活性。与传统的强酸催化剂相比,[n-C6Im][HSO4]具有合成的PEAC色泽好、催化剂易回收与重复利用的优点。     

N-甲基吡咯烷酮硫酸氢盐催化合成己二酸二异辛酯

以新型离子液体N-甲基吡咯烷酮硫酸氢盐([Hnmp]HSO4)为催化剂,己二酸和异辛醇为原料,环己烷为带水剂,对己二酸二异辛酯的酯化反应进行了研究,重点考察了醇酸摩尔比、催化剂用量、带水剂加入量、反应时间等因素对己二酸二异辛酯酯化率的影响。实验结果表明,N-甲基吡咯烷酮硫酸氢盐对合成己二酸二异辛酯有着良好的催化活性,当己二酸用量为0.1mol时,醇酸摩尔比为2.6:1,催化剂用量为己二酸物质的量的1.2%,带水剂环己烷为10mL,回流温度下反应时间120min,在此条件下,反应的酯化率可达99%以上,且催化剂重复使用6次仍保持较高活性。     

酸性离子液体催化制备1,2-甘油二酯

考察了4-(3-磺丙基)-吗啡啉硫酸氢盐([C3SO3Hnhm]HSO4)、吗啡啉硫酸氢盐、N-甲基-2-吡咯烷酮硫酸氢盐、N-甲基咪唑硫酸氢盐和N-甲基咪唑对甲苯磺酸盐等五种酸性离子液体在苯甲酸和甘油,苯甲酸、乙酸和甘油的酯化反应体系中的催化活性,获知磺酸基功能化的[C3SO3Hnhm]HSO4的催化活性最高。酯化产物2-乙酰氧基-3-羟丙基苯甲酸酯采用1H NMR和FTIR法进行了结构表征并确认。基于产物结构,采用1H NMR法定量。[C3SO3Hnhm]HSO4用作催化剂时,以苯甲酸、乙酸和甘油为原料制备2-乙酰氧基-3-羟丙基苯甲酸酯反应的条件优化结果表明,n(乙酸)︰n(苯甲酸)︰n(甘油)︰n(离子液体)=3.4︰2︰1︰0.27,苯甲酸和甘油在120℃反应4 h后加入乙酸继续反应3 h,2-乙酰氧基-3-羟丙基苯甲酸酯的产率可达74.0%,并且产物易于分离,后处理简便。不经任何处理的离子液体可重复使用2次,催化的活性基本不变。     

离子液体催化反应精馏合成乙酸乙酯工艺模拟

为研究离子液体在反应精馏中的作用,采用离子液体1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）作为催化剂,对乙酸和乙醇合成乙酸乙酯的反应精馏流程进行了计算模拟。在确定了参数的酯化反应动力学的基础上,用Aspen Plus软件建立了反应精馏流程,研究了催化剂用量、精馏段理论板数、反应段理论板数、乙醇进料位置、进料摩尔比、持液量及回流比等参数对反应精馏过程的影响。研究结果表明,塔顶乙酸乙酯的质量分数随催化剂用量、精馏段理论板数、反应段理论板数和持液量增大而增大,工艺流程存在最佳回流比以及最佳进料酸醇摩尔比。得到的优化条件如下：离子液体与乙酸摩尔比为1：2.5,进料酸醇摩尔比为4：1,理论塔板数为21块,乙酸和催化剂在第7块理论塔板进料,乙醇在第19块理论塔板进料,塔板持液量0.1L,回流比为4,塔顶乙酸乙酯的质量分数可以达到98.73%。     

N-甲基吡咯烷酮硫酸氢盐催化合成7-羟基-4-甲基香豆素

以离子液体N-甲基吡咯烷酮硫酸氢盐为催化剂,通过Pechmann缩合反应于无溶剂条件下合成了7-羟基-4-甲基香豆素,实验表明N-甲基吡咯烷酮硫酸氢盐可重复使用并具有较好的催化活性。在原料摩尔比n(间苯二酚)∶n(乙酰乙酸乙酯)为1∶1.3、催化剂[Hnmp]HSO4占反应物料总质量的1.2%、回流反应时间3 h的条件下,产品收率达87.24%,经液相色谱分析纯度大于98.5%。     

酸性离子液体催化合成季戊四醇棕榈油酸酯

合成两种酸性离子液体,正丁基甲基咪唑硫酸氢盐[n-C4Im][HSO4]和异丁基甲基咪唑硫酸氢盐[i-C4Im][HSO4],催化合成季戊四醇棕榈油酸酯(PPAE),结果发现[i-C4Im][HSO4]催化活性最大。通过对影响转化率的各种因素考察,得到最佳反应条件:棕榈油酸与季戊四醇物质的量比为6∶1,离子液体催化剂用量5%(质量分数),反应温度220℃,反应时间4 h,PPAE转化率为91.8%。离子液体催化剂重复使用2次后,转化率开始缓慢下降,但补充适量硫酸后离子液体即可恢复催化活性。与传统的强酸催化剂相比,[i-C4Im][HSO4]具有合成的PPAE色泽好、催化剂易回收与重复利用的优点。     

新型酸功能化离子液体催化合成柠檬酸三丁酯的研究

研究了酸功能化离子液体1-（4-磺酸基）丁基-3-甲基咪唑磺酸盐[（CH2）4SO3Hmirn]HSO4、1-（4-磺酸基）丁基吡啶硫酸氢盐[（CH2）4SO3HPy]HSO4及1-（4-磺酸基）丁基三乙胺硫酸氢盐[（CH2）4SO3HTEA]HSO4催化柠檬酸三丁酯的合成.系统考察了反应时间、酸与醇的配比、催化剂的用量、不同阳离子、不同阴离子等因素对反应的影响及催化剂重复使用性,优化了反应条件.得到较佳工艺条件为∶当酸与醇摩尔比为1∶4.5,催化剂用量为反应物总质量的2％,反应4h,酯化率可达99％以上.分离出的离子液体未经任何处理重复使用5次后,酯化率仍可为89.5％.     

离子液体催化合成乙酸苄酯

以硫酸氢根甲基咪唑盐[Hmim]HSO_4离子液体为催化剂,乙酸和苯甲醇为原材料通过催化反应来合成乙酸苄酯,同时还讨论了以浓硫酸作为催化剂合成乙酸苄酯的方法。通过各个不同条件的实验,涉及的可变因素有酸醇物质的量比、催化剂用量、反应时间、反应温度等。实验结果表明,硫酸氢根甲基咪唑盐[Hmim]HSO_4对合成乙酸苄酯有着良好的催化活性,而且对其合成工艺进行了优化,确定最佳反应条件为:酸醇的摩尔比为1.4∶1、催化剂用量1%、反应温度110℃、加热回流1 h。在此条件下,乙酸苄酯的酯化率达96%。     

酸功能化离子液体催化合成马来酸二异辛酯

合成了4种酸功能化离子液体,由IR、1HNMR对其结构进行了确证,并将其用于催化合成马来酸二异辛酯。结果表明,以离子液体[HSO3-pMIM]HSO4为催化剂,n(马来酸酐)∶n(异辛醇)=1∶2.2,马来酸酐0.1 mol,催化剂用量2.3 g,回流反应2.0 h条件下,马来酸酐酯化率达98.5%。且该离子液体与反应产物易于分离。反应后的离子液体[HSO3-pMIM]HSO4未经处理可重复使用7次,酯化率仍高于97.5%,第7次使用后用水萃取,其回收率为68.5%,补加至第一次用量再次进行实验,得酯化率为98.5%。     

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。