N-异冰片基丙烯酰胺的合成

以丙烯腈和天然可再生资源莰烯为原料,在无溶剂条件下催化合成了N-异冰片基丙烯酰胺(NIBAM)。探索了催化剂种类及用量、物料配比、反应温度、反应时间对反应选择性和NIBAM得率的影响。采用正交实验确定了适宜的合成工艺条件:以FeCl3为催化剂,含量为10%(以莰烯、丙烯腈和水的总质量计,下同),n(莰烯)∶n(丙烯腈)∶n(水)=1∶3∶1,反应温度120℃,反应时间12 h。在此条件下,NIBAM选择性和得率分别为97.6%和90.3%。此外,采用HRMS、FTIR和NMR等分析技术对产物结构进行了确证。     

异龙脑基乙醚的合成研究

工业莰烯在耐高温离子交换树脂DCP催化作用下与无水乙醇反应生成了异龙脑基乙醚。探索了反应温度、反应时间、催化剂用量,以及工业莰烯与无水乙醇的配比对反应的影响。结果表明,异龙脑基乙醚合成的优化条件为:m(工业莰烯):m(无水乙醇)=10:7~10:9, DCP用量占物料总质量的 15%,反应温度(75±1)℃ ,反应时间6~9 h,工业莰烯转化率达到 71.5%,选择性达到 96.8%。     

氯化锌直接催化α-蒎烯异构制备莰烯反应规律研究

研究了以无机氯化物为催化剂催化α-蒎烯异构制备莰烯的反应规律,考察了催化剂种类、催化剂用量、反应时间、反应温度对异构反应的影响,确定了最佳的反应条件。在最佳反应条件下,即以氯化锌(ZnCl2)为催化剂,用量占α-蒎烯质量的3%,α-蒎烯用量2.86g,温度140℃,反应时间10h,α-蒎烯异构化反应转化率为94.64%,莰烯选择性为50.42%。     

响应面法优化微波辐射合成甲基丙烯酸异冰片酯

以莰烯和甲基丙烯酸为原料,采用微波辐射法合成了甲基丙烯酸异冰片酯(IBOMA),通过FTIR及1HNMR对产物的结构进行了表征,在微波反应时间、反应温度、微波功率、莰烯与甲基丙烯酸物质的量比及催化剂Amberlyst15用量等单因素实验基础上,通过Design Expert8.0中的中心响应面法对反应条件进行了优化,确定最佳合成工艺为:催化剂用量为10%(以莰烯与甲基丙烯酸总质量为基准)、n(莰烯)∶n(甲基丙烯酸)=1.0∶0.8、微波反应时间25 min、反应温度43℃、功率为400 W。在此工艺条件下,IBOMA的酯化率可达到82.83%。     

用强酸树脂催化合成高含量乙酸异龙脑酯

采用强酸型离子交换树脂（干氢型）为催化剂,通过改变反应条件（温度、时间、配比）,研究了莰烯与醋酸酯化反应制备含量大于94%的乙酸异龙脑酯的适宜条件,结果表明：莰烯与醋酸催化合成高含量乙酸异龙脑酯的适宜工艺条件为：反应时间2～3h、反应温度30～35℃、莰烯与醋酸的质量比1.88～1.90。上述反应条件下可以得到含量约72%的粗酯,粗酯再通过精馏,可以得到净酯含量约95%的乙酸异龙脑酯。     

微波辐照下MoO3／ZrO2催化合成甲酸异龙脑酯

本文采用在微波辐照下,以自制MoO3/ZrO2型固体超强酸为催化剂,通过改变微波功率、时间、催化剂焙烧温度及用量等条件,研究了莰烯与甲酸反应转化为甲酸异龙脑酯的工艺。实验结果表明:酯化反应的适宜工艺条件为:莰烯与甲酸摩尔比为1∶1.2,微波功率320W,反应时间75min,催化剂焙烧温度为700℃,用量为莰烯质量的5%。在上述条件下,甲酸异龙脑酯收率80.2%。     

过氧磷钼钨酸盐高效催化3-蒈烯氧化合成3,4-环氧蒈烷

以过氧磷钼钨酸十六烷基吡啶盐Cat-PMo2W2O24为催化剂,质量分数为30%的H2O2为氧化剂,催化3-蒈烯选择性环氧化合成3,4-环氧蒈烷。系统考察了溶剂种类、反应温度、催化剂用量、H2O2用量及反应时间对底物转化率与环氧选择性的影响,确定了最佳反应条件为：3-蒈烯12 mmol,溶剂三氯甲烷5 ml,催化剂用量为2.45 %（以3-蒈烯的质量百分数计）,H2O2与3-蒈烯物质的量的比值为1.1,反应温度35 ℃,反应时间6 h;在最佳条件下,3-蒈烯的转化率和3,4-环氧蒈烷的选择性分别为99.1 %和94.8 %。     

SO_4~(2-)/TiO_2负载磷钨酸型固体酸制备乙酸异龙脑酯

TiCl_4水解同时加入磷钨酸,氨水沉淀后,采用硫酸铵混合后焙烧工艺制备了SO_4~(2-)/TiO_2负载磷钨酸型固体酸催化剂。用乙酸和莰烯进行反应合成乙酸异龙脑酯,对反应时间、催化剂用量、莰烯与乙酸物质的量比、反应温度进行了优化实验,采用气相色谱法进行产品检测。结果表明反应酸烯物质的量比为2:1、催化剂用量为酸烯总质量的3%、反应6h、反应温度80℃的条件下转化率最高,可达85.5%,经初步蒸馏后产品纯度可达95%以上。     

AlCl_3-丙三醇络合催化剂催化1-辛烯齐聚工艺

以1-辛烯为原料,A1C13/丙三醇络合物为催化剂,催化1-辛烯齐聚反应,合成α-烯烃。考察了络合催化剂的添加量、反应温度、反应时间、丙三醇与AlCl3的摩尔比对聚α-烯烃（PAO）收率的影响。结果表明,在AlCl3摩尔分数为4%,丙三醇与AlCl3的摩尔比为0.5,反应温度为40℃,反应时间为4 h的条件下,PAO收率达到85.6%,且具有较好的选择性。     

碳酸钾催化酯交换合成碳酸二丁酯的研究

研究了碳酸二甲酯（DMC）与正丁醇（n-BuOH）酯交换合成碳酸二正丁酯（DBC）的反应，筛选出合成碳酸二正丁酯的催化剂。考察了物料配比、温度和时间诸因素对反应的影响。结果表明，K₂CO₃具有较好的催化活性和选择性。得出了该反应最佳工艺条件：常压，反应温度140 ℃，反应时间4 h，n(DMC)∶n(n-BuOH)=1∶3。在催化剂用量为原料总质量的1%的条件下，DMC转化率为89.1%，DBC收率为86.9%，DBC选择性为97.6%，甲基丁基碳酸酯（MBC）收率为2.2%，碳酸二异丁酯(DIBC)的收率为70.0%，碳酸二叔丁酯（DTBC）收率为10.3%。     

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.     

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.     

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。     

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.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.