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.     

MCM-41分子筛的制备及催化性能研究

用微波法合成MCM-41中孔分子筛.并采用液相沉积法制备了以MCM-41分子筛为载体负载TiO2/S2O82-的同体酸催化剂,以乙酸与异戊醇的酯化反应作为探针反应,考察了焙烧温度、焙烧时间、浸渍溶液的浓度、浸渍时间以及钛硅比等制备条件对催化剂催化活性的影响,得到了最佳的制备条件.最佳条件是:n(Ti)/n(Si)=2,...     

MCM-41负载氧氮化钼的制备和表征

将MoO3和介孔材料MCM-41的机械混合物热处理得到MoO3／MCM-41复合体，将MoO3／MCM-41在氨气氛中于700℃氮化处理3h，制备了氧氮化钼负载的MCM-41催化材料。用XRD，XPS和氮吸附-脱附等手段表征了该材料。结果表明：在XRD图谱中出现氧氮化钼的微弱衍射峰，证明通过这种方法得到的材料中的氧氮化钼呈现结晶趋势。XPS谱表明：Mo存在多种化学状态。氧氮化钼负载的MCM-41的比表面积，孔体积和孔径等参数小于MoO3／MCM-41和纯MCM-41的值。     

采用负载铁的介孔分子筛催化模板剂合成多壁碳纳米管

用水热法合成纯硅介孔分子筛(mesoporous molecular sieves,MCM-41)。用浸渍法将MCM-41负载不同量铁制得负载铁的介孔分子筛(Fe-loading mesoporous molecular sieve,Fe/MCM-41)。以Fe/MCM-41作为催化剂催化热解乙醇制备碳纳米管。用N2物理吸附、Raman光谱、透射电镜和高分辨透射电镜等手段对样品进行了表征。结果表明:制备出了多壁碳纳米管,并且随着催化剂中Fe负载量的增加,所生成碳纳米管的管径增加。     

不同负载方式Fe/改性MCM-41催化剂的制备及其降解亚甲基蓝性能研究

以自制二元共聚物聚[苯乙烯—3-（甲基丙烯酰氧）丙基三甲氧基硅烷]改性MCM-41,并以其为载体分别采用浸渍负载活性金属、原位负载活性金属和NaBH₄还原负载活性金属的方式制备铁基异相催化剂。研究了3类催化剂降解亚甲基蓝的性能差异。结果显示,在3种催化剂中,浸渍负载活性金属制备的催化剂具有最好的催化活性,25 min时亚甲基蓝去除率为81.2%。同时采用XRD、TEM、FTIR、XPS、压汞测试等手段分析了催化剂具有优异性能的原因。表征结果表明:Fe与改性MCM-41间的相互作用及催化剂孔结构,两者的协同作用是催化剂具有优异性能的原因。     

MCM-41负载Pt-Al催化剂的制备及其表征

以介孔硅MCM-41为载体、无水乙醇为溶剂、氯化铝为促进剂,采用浸渍法制备了Pt-Al/MCM-41催化剂。利用XRD、XPS、TEM、FTIR、N_2吸附-脱附、NH3-TPD对催化剂进行了表征,重点讨论了不同Pt-Al负载顺序对催化剂结构和性能的影响,并将其应用于硅氢加成反应。结果表明,Pt和Al的负载顺序不同会影响催化剂的有序度、Pt颗粒的分散程度和酸性,其中,Pt-Al/MCM-41催化剂的有序度和Pt颗粒的分散程度相对最好,酸性相对较强。在七甲基三硅氧烷与烯丙醇聚氧乙烯醚的硅氢加成反应中,不同催化剂对七甲基三硅氧烷的转化率影响顺序为Pt-Al/MCM-41Pt+Al/MCM-41Al-Pt/MCM-41Pt/MCM-41。     

MCM-41负载Pt-Al催化剂的制备及其表征

以介孔硅MCM-41为载体、无水乙醇为溶剂、氯化铝为促进剂,采用浸渍法制备了Pt-Al/MCM-41催化剂。利用XRD、XPS、TEM、FTIR、N₂吸附-脱附、NH₃-TPD对催化剂进行了表征,重点讨论了不同Pt-Al负载顺序对催化剂结构和性能的影响,并将其应用于硅氢加成反应。结果表明,Pt和Al的负载顺序不同会影响催化剂的有序度、Pt颗粒的分散程度和酸性,其中,Pt-Al/MCM-41催化剂的有序度和Pt颗粒的分散程度相对最好,酸性相对较强。在七甲基三硅氧烷与烯丙醇聚氧乙烯醚的硅氢加成反应中,不同催化剂对七甲基三硅氧烷的转化率影响顺序为Pt-Al/MCM-41 > Pt+Al/MCM-41 > Al-Pt/MCM-41 > Pt/MCM-41。     

P-MCM-41对负载型钼基催化剂上丁烯自歧化制丙烯的影响

近年来,丙烯下游产品的快速发展极大的促进了丙烯需求量的增长。通过1-丁烯自歧化反应生成丙烯可以实现低价值烯烃向高价值烯烃的转换。采用水热法制备了一系列P掺杂MCM-41为载体,并用湿法浸渍负载氧化钼的催化剂,在固定床反应器上对催化剂进行1-丁烯自歧化产丙烯反应性能评价。采用XRD、N_2吸附-脱附、吡啶吸附红外光谱、H_2-TPR和NH_3-TPD等对催化剂进行表征。结果表明,与2%Mo/MCM-41相比,P掺杂MCM-41为载体,可以使催化剂上氧化钼物种分散程度提高,并使催化剂具有一定程度的酸性,提高了1-丁烯自歧化反应的活性和稳定性。2%Mo/5P-MCM-41具有最高的歧化活性,丁烯转化率为65.9%,丙烯收率为21.7%。     

MCM-41介孔分子筛负载咔唑类荧光分子杂化材料的合成及发光性质

通过浸渍法将5种咔唑类荧光分子负载于介孔材料MCM-41上,制备有机-无机杂化复合荧光材料,并对咔唑荧光分子和杂化复合材料的表面结构、紫外-可见吸收、荧光发射等性质进行了对比。结果表明,负载后的咔唑类荧光分子分散于MCM-41孔道上,材料热稳定性提高,在100~350℃内没有明显失重,其紫外吸收和荧光发射也发生明显蓝移(λmaxabs=331~368 nm,λmaxem=401~435 nm)。制备的杂化复合材料可用作蓝色荧光材料(λmaxem=401~435 nm)。     

PEI-MCM-41吸附剂的制备及其CO_2吸附性能研究

使用不同方法合成了MCM-41,制备出具有不同骨架结构和内部孔道结构的介孔分子筛。通过XRD、高倍投射电镜、低温氮吸附/脱附等方法对样品进行了表征分析。用PEI对MCM-41分子筛进行改性,然后使用热重方法测定了其对CO2的吸附量。结果表明,使用硅酸钠和硫酸为原料制备的样品具有较大的比表面积和孔容,在该样品上负载50%PEI吸附量达到了269.3 mg/g,是同等条件下单纯PEI吸附量的3.4倍。说明将PEI负载在具有大比表面积和孔容的MCM-41介孔分子筛上,可以使PEI得到充分分散,并充分利用PEI分子上的氨基。     

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。