Pd/Fe3O4催化剂的制备及在Suzuki偶联反应中的应用

利用浸渍法制备Pd/Fe3O4负载型磁性纳米催化剂。通过透射电镜(TEM)、X射线衍射(XRD)、电感耦合等离子体-发射光谱(ICP)及振动样品磁强计(VSM)等物理化学手段对其进行了表征。将Pd/Fe3O4催化剂应用于卤代芳烃与芳基硼酸的Suzuki偶联反应中。研究结果表明:Pd/Fe3O4催化剂具有一定的磁性,利用外磁场可方便快速地分离出催化剂。负载Pd的质量分数为12.01%时,催化活性最高;在空气中,无需在惰性气体的保护下能有效地催化芳基硼酸与卤代芳烃的Suzuki偶联反应,催化剂重复使用5次后,催化活性没有明显的降低。     

易磁分离钯催化剂的合成及应用研究

合成了氨基稳定的、易回收再使用的磁性纳米Fe3O4负载钯催化剂,该催化剂对溴苯与苯硼酸的Suzuki偶联反应具有高的催化活性.研究结果表明:在40℃催化反应2h,联苯产率达97％,催化剂连续使用3次,催化活性基本保持不变.     

柳树叶提取液还原制备水滑石负载纳米钯催化剂及催化Suzuki反应

以柳树树叶提取液作为还原剂和稳定剂,制备了水滑石负载纳米钯催化剂(Pd/HT)。采用IR、XRD、TEM、N-2吸附脱附等手段对制备的催化剂进行了表征,并研究了其催化Suzuki偶联反应的性能。表征结果显示:制备的Pd/HT中钯纳米粒子分散均匀,粒径分布较窄,平均粒径为3.8nm。提取液中的生物质不仅起到还原作用,而且还起到稳定钯纳米粒子的作用。催化Suzuki偶联反应结果表明:Pd/HT表现出优良的催化活性,重复使用5次,催化活性没有明显降低。     

磁性纳米负载金属催化剂的制备及其在甲苯催化氢化反应中的性能

通过化学共沉淀法制备了Fe3O4,以硅酸钠、铝酸钠为原料,碳分法原位对其进行表面包覆,制备出具有核壳结构的SiO2/Fe3O4及Al2O3/SiO2/Fe3O4复合磁性纳米粒子。利用XRD、SEM、FTIR以及VSM技术对其进行了表征。将所制备的这两种磁性载体分别负载金属Ru及Ru-Co催化剂,以甲苯为底物考察了负载催化剂的组成与催化加氢活性的关系。结果表明,以SiO2/Fe3O4为载体负载的催化剂具有很好的催化活性,循环使用6次后活性未下降;以Al2O3/SiO2/Fe3O4为载体所负载的催化剂,起始催化活性较高,循环过程中活性略微降低。双金属Ru-Co催化剂的催化性能与其形成的结构及组成密切相关,催化活性为RushellCocoreRu-CoCoshellRucore,Ru/Co的摩尔比为1∶5的RushellCocore/PVP/SiO2/Fe3O4催化剂对甲苯有较高的催化活性,催化剂的转化频率可达16656,高于相同条件下的单金属Ru催化剂的转化频率(9828)。     

Ni-Fe/BaTiO3-γ-Al2O3催化剂在低温条件下CO2和CH4重整中的应用

采用等体积浸渍法制备了一系列不同Ni和Fe添加量的Ni-Fe/BaTiO3/γ-Al2O3双金属催化剂,并在固定床反应装置上考察了在873～1 073 K温度范围内催化剂对CO2和CH4重整反应的催化活性。实验结果表明:Ni、Fe负载质量分数均为5.0%的Ni-Fe/BaTiO3/γ-Al2O3催化剂活性最好。通过TPR、TPD和TPO表征并与单金属催化剂Ni/BaTiO3/γ-Al2O3相比,Ni-Fe/BaTiO3/γ-Al2O3催化剂具有更高的催化活性、脱附和抗积炭性能。     

微波辅助法制备钯纳米粒子及其催化Suzuki反应的研究

以柠檬酸为还原剂,在PVP保护下通过微波辅助法制备了钯纳米粒子(Pd NPs)催化剂,并通过UV-Vis、TEM、XRD等分析手段对其进行表征。考察了碱和溶剂的种类、溶剂与水的比例及反应温度对Suzuki偶联反应的影响。优化后的反应条件为,K2CO3为碱,溶剂为Et OH/H2O(体积比6∶6)、反应温度为60℃。在Pd NPs的用量为0.1mmol‰催化对溴甲苯与苯硼酸的Suzuki偶联反应中,反应30min产物收率达到99%。     

不同氧化物载体对于钯催化苯甲醇与苯胺偶联反应的影响

醇与胺类化合物的偶联反应是构建含氮有机化合物的重要方法,本文考察了不同过渡金属氧化物作为催化剂载体,通过浸渍法负载上Pd,并进一步测试了在苯甲醇和苯胺偶联反应中的催化效果,发现Pd/Ni2O3可以得到最高的产率。     

双溶剂法制备Pd/MIL-100及其催化Suzuki偶联反应的研究

采用溶剂热法合成了MIL-100(Cr),通过双溶剂浸渍法负载Pd纳米粒子制备负载型Pd/MIL-100催化剂。以溴苯与苯硼酸偶联合成联苯为模型反应,考察了溶剂、碱助剂、温度等因素对Suzuki偶联反应性能的影响。结果表明,以V(EtOH)∶V(H₂O)=2∶1为溶剂、K₂CO₃为碱助剂,在60℃反应0.5 h,溴苯转化率达到97%,目标产物联苯选择性>99%;催化剂对于对位和间位供电子基团取代的芳基硼酸具有良好的底物适用性;Pd/MIL-100催化剂循环使用3次仍保持良好的催化活性及稳定性。XRD、XPS、ICP及TEM表征结果表明,催化剂失活的主要原因是由于Pd纳米粒子在MIL-100表面发生了迁移团聚。     

PVP保护制备水滑石负载纳米Pd催化剂及催化Suzuki反应中的应用

以水滑石(HT)为载体,在PVP保护下,制备了可重复使用的负载型纳米钯催化剂(Pd/HT)。通过UV-Vis、XRD、TEM、XPS等分析手段,对制备催化剂的结构进行了表征。分析结果表明:制备的Pd/HT结构稳定,钯纳米粒子平均粒径4nm左右,且分散均匀。考察了碱、溶剂、反应时间、反应温度等条件对Pd/HT催化Suzuki反应结果的影响。实验结果表明:当Pd/HT催化剂Pd的物质的量用量只为反应底物的0.5‰时,催化不同底物偶联反应的收率最高可达98.84%,反映出很高的催化活性。     

离子液体在Suzuki偶联反应中的应用

过渡金属Pd催化的Suzuki偶联反应是构建C-C键的重要反应之一,在许多领域都有着广泛应用.在离子液体中进行的Suzuki偶联反应具有反应活性高、选择性好等特点.含有Pd配体的功能化离子液体直接催化Suzuki偶联反应可提高催化活性,容易实现产物与催化剂分离.固载化离子液体可有效地解决催化剂难以重复使用的问题.     

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。