VMCM-41对环己烷选择性氧化的研究

以十六烷基三甲基溴化铵为模板剂,水玻璃为硅源,在55℃水热条件下合成出介孔VMCM—41分子筛。以VMCM—41分子筛为催化剂,H2O2为氧源,研究了反应温度、时间、引发剂等因素对环己烷选择性氧化的影响。结果表明,在以环己酮为引发剂的情况下,VMCM—41是一种温和、高效的环己烷选择性氧化催化剂。     

环己烷催化氧化制环己酮的MCM-41催化剂研究

以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,采用水热合成法制备纯MCM-41分子筛和掺杂不同金属离子的MCM-41分子筛,并采用等体积浸渍法将一定量的金属离子负载在纯MCM-41分子筛内表面上,制备了负载型和掺杂型2类不同的MCM-41分子筛催化剂.分别考察了负载和掺杂的金属种类、金属Cr负载和掺杂量等对环己烷氧化制环己酮中的催化活性和选择性的影响.研究表明:采用掺杂制备的MCM-41分子筛催化剂活性明显高于负载型MCM-41分子筛催化剂;Cr掺杂量增加,虽然环己烷氧化转化率增加,但产物选择性下降;掺杂Cr的MCM-41分子筛催化剂,用于环己烷氧化制环己酮,在Si与Cr摩尔比为50以下、反应温度75℃、H2O2与环己烷摩尔比为1.2的条件下,环己烷的转化率可达60%左右,环己酮和环己醇的总选择性可达94%以上.     

分子筛固载型Cosalen的制备、表征及其应用研究

分别采用NaY分子筛、γ-氨丙基三乙氧基硅烷修饰的MCM-41分子筛固载双水杨醛缩乙二胺合钴(Cosahn)配合物,制备了固载型Cosahn/NaY、Cosalen/MCM-41催化剂.采用傅里叶变换红外光谱、热重-差热、X射线衍射、比表面积测定等方法对固载型分子筛催化剂的结构进行表征.结果表明,Cosalen已成功地进入分子筛孔道内.在以氧气为氧源的环己烷氧化反应中,Cosalen/MCM-41催化剂具有较好的活性和对环己醇、环己酮的选择性.该催化反应体系产物中环己基过氧化氢(CHHP)的量很少,表明Cosalen/MCM-41催化剂能加速CHHP的分解.在初始氧气压力0.80 MPa、温度130℃、环己烷用量30 g、Cosalen/MCM-41用量0.30 g、叔丁基过氧化氢0.10 g的条件下反应2 h,环己烷的转化率达到5.96%,醇酮选择性87.03%.     

环己烷催化氧化催化剂的研究进展

综述了国内外环己烷选择性氧化催化剂的研究进展,对目前环己烷氧化所用催化剂体系进行了总结及比较分析,重点介绍了分子筛催化剂体系中TS-1、MCM、SBA-15等分子筛催化体系.     

纳米金复合催化剂制备及其低温选择催化环己烷氧化性能

采用光催化直接还原法将Au(0)负载在TiO2修饰的中孔分子筛MCM-41的孔道内外,采用XRD, N2吸附-脱附,FT-IR, TEM和EDS等手段对所制催化剂进行了表征,并考察了其在温和条件下对环己烷选择性氧化反应的催化性能. 结果表明,所制纳米金催化剂的分子筛载体仍具有较高的结晶度,金颗粒粒径在10 nm左右. 在环己烷氧化反应中,纳米金与TiO2光催化共同作用,使复合催化剂具有低温高催化活性. 在温度100℃、压力1.0 MPa及250 W紫外灯光照8 h的条件下,环己烷转化率高达3.9%,目的产物的总选择性为90.2%.     

分子氧氧化环己烷制环己酮催化剂的研究进展

综述了分子氧氧化环己烷制取环己酮的催化剂的研究进展,重点介绍了光催化剂、纳米催化剂、仿生催化剂、分子筛催化剂和复合催化剂在环己烷催化氧化方面的应用,其中,负载在分子筛上的纳米金催化剂具有较高的催化活性、选择性及稳定性。     

杂原子MCM-41分子筛的合成及对环己烷氧化的研究

用十六烷基三甲基溴化铵为模板剂,水玻璃为硅源,在合成过程分别加入Cr3+、Co2+、Fe3+杂原子,在150℃晶化48h,水热合成了Cr-MCM-41、Co-MCM-41、Fe-MCM-41等杂原子分子筛。考察了时间、温度、催化剂用量、过氧化氢用量及催化剂再生等因素对环己烷氧化反应的影响。最佳反应条件为:温度100℃;环己烷30mmol,Cr-MCM-41为催化剂,用量0 12g;n(H2O2)/n(C6H12)=1;反应时间16h,环己烷的转化率可达28 6%,产物的酮醇摩尔比为1 89。     

FeAPO-5分子筛的表征及其催化环己烷氧化性能

以三乙胺为模板剂,用水热晶化法合成了FeAPO-5分子筛,并用X射线衍射(XRD)、程序升温还原(TPR)、热重分析(TG)、傅立叶红外光谱(FT-IR)和紫外-可见漫反射光谱(UV-Vis DRS)等对分子筛样品进行了表征.结果表明,铁原子通过同晶取代方式进入分子筛骨架,结晶度高,晶粒均匀.以FeAPO-5为催化剂,氧气为氧源,叔丁基过氧化氢为引发剂,在反应温度为130 ℃和压力1.5 MPa条件下,反应24 h,环己烷转化率为6.52%,醇酮总选择性可达96%以上,酮醇比达3.34,几乎没有环己基过氧化氢生成.     

微通道反应器中环己烷液相氧化反应工艺的研究

以纯氧为氧化剂、环己酮为引发剂和环烷酸钴(II)为催化剂,研究了内径为0.762 mm、长度为20 m的微通道反应器内环己烷液相氧化的反应行为,考察了表观气体流速、表观液体流速、反应温度、压力和催化剂用量等因素对环己烷转化率和产物选择性的影响。在氧气和环己烷表观流速分别为1.80 m?s-1和0.004 m?s-1、温度165℃、压力1.4 MPa、环己酮加入量0.2%(wt)和催化剂钴(II)浓度为10 ppm时,环己烷的转化率为4.57%,环己醇、环己酮和环己基过氧化氢的选择性分别为61.72%、34.87%和1.12%,己二酸的选择性小于3.0%。结果表明,微通道反应器中进行环己烷液相催化氧化,能有效提高气液相界面积,加快环己烷氧化反应速率,降低副产物的生成。     

环己烷一步氧化法制己二酸的催化剂研究进展

概述了环己烷两步氧化法和一步氧化法制己二酸工艺,传统的两步氧化法存在工艺流程复杂,能耗高,环境污染严重等问题,环己烷一步氧化法采用了绿色多相催化剂代替低活性催化剂硝酸;介绍了国内外环己烷一步氧化法制己二酸的催化剂研究进展,其中重点介绍了锰/钴类、分子筛类、负载型纳米金类、仿生类等催化体系;经过对比发现负载型纳米金催化剂具有优异的催化活性和选择性,指出负载型纳米金催化剂具有巨大的应用潜力,纳米金材料和碳材料相结合一步法制己二酸工艺值得进一步研究。     

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。