Pd/rGO催化硝基苯无溶剂加氢合成苯胺

采用氧化石墨烯（GO）、还原石墨烯（rGO）和硝酸活化处理的活性碳（C-HNO3）负载Pd纳米粒子制得了3种Pd基催化剂Pd/GO、Pd/rGO和Pd/C-HNO3。通过XRD、XPS、N2吸附-脱附、SEM、TEM、HRTEM对其进行了表征。以商用Pd/C催化剂（Pd质量分数10%）作为对照，考察3种催化剂催化硝基苯无溶剂加氢的活性和选择性。结果表明，rGO纳米片高效网络结构和Pd纳米粒子之间的良好的耦合作用使得Pd/rGO在3种催化剂中表现出最高的Pd金属比表面积（178.37 m2/g）和分散度（43.75%）。在Pd/rGO催化剂质量浓度为10 g/L，1 MPa H2，90 ℃，5 mL 硝基苯的反应条件下，苯胺的产率随反应时间增加呈上升趋势。反应100 min后，硝基苯完全转化，苯胺产率达到100%。循环使用9次后，Pd/rGO仍可催化硝基苯高效转化获得97.1%的苯胺产率。     

单分散氮掺杂的碳纳米球负载钯催化氯代硝基苯加氢反应

高效钯炭催化剂的研制是卤代硝基苯选择性加氢还原制备卤代苯胺工艺取得突破的关键。以单分散氮掺杂的碳纳米球为载体、钯为活性组分,采用浸渍法制备出负载型的Pd/CN-x(x代表碳基载体的焙烧温度),并对其催化氯代硝基苯加氢制备氯代苯胺反应的性能进行了研究。分别采用傅里叶变换红外光谱(FT-IR)、X射线衍射光谱(XRD)、透射电子显微镜(TEM)、场发射扫描电镜(SEM)以及X射线光电子能谱(XPS)技术对Pd/CN-x催化剂的形貌、结构及表面化学性质进行了表征分析。考察了不同温度下制备出的碳氮材料负载钯催化剂对氯代硝基苯选择性加氢还原反应活性和选择性的影响。研究结果表明,以单分散氮掺杂的碳纳米球为载体能够实现金属Pd颗粒的均匀分散,因而催化剂表现出优异的催化加氢性能。其中,Pd/CN-600催化剂表现出100%的3-氯硝基苯转化率,同时对3-氯苯胺的选择性高达76.9%。此外,载体表面含氮官能团影响活性Pd组分的有效分散,进而影响3-氯苯胺的选择性。     

Pd亚纳米簇@SiO2催化芳香硝基化合物加氢制芳胺

以新配制的硝酸钯溶液为原料，在十六烷基三甲基溴化铵/正丁醇/环己烷形成的反相微乳液体系中采用一锅法制备Pd亚纳米簇@SiO2核壳材料，得到质量分数达4%（以SiO2的质量计）、平均粒径为0.7 nm的Pd亚纳米簇。采用TEM、XRD、XPS、N2吸附-脱附对材料的物化性质进行了表征，探讨了其对芳香硝基化合物加氢制芳胺反应的催化性能。结果表明，在温和的反应条件下（50 ℃、1.0 MPa H2），催化剂Pd亚纳米簇@SiO2上硝基苯加氢反应4 h，苯胺的收率高达99.5%。在该催化剂上，其他多种芳硝基化合物加氢反应同样获得了较高的芳胺收率（98.5%~100%）。催化剂Pd亚纳米簇@SiO2循环4次后，活性无明显下降。     

一种具有温敏表面的氧化石墨烯负载钯催化剂的制备及催化性能

以过硫酸铵（APS）为引发剂,N-异丙基丙烯酰胺（NIPAM）为单体,在氧化石墨烯（GO）表面生长温敏高分子聚（N-异丙基丙烯酰胺）（PNIPAM）,获得复合载体GO-PNIPAM,并通过水相浸渍还原法制备具有温度敏感特性的Pd催化剂（Pd/GO-PNIPAM）。采用红外光谱、差示量热、热重、元素分析、透射电镜和电感耦合等离子原子发射光谱对复合载体GO-PNIPAM和Pd催化剂进行表征。结果表明,PNIPAM在GO上的接枝率约占60%。GO-PNIPAM显示出明显的温敏效应,其最低临界溶液温度约37℃。Pd/GO-PNIPAM上Pd纳米颗粒的平均粒径为(4.70±0.85)nm,远小于Pd/GO中Pd平均粒径(8.79±2.68)nm。因此,PNIPAM在GO上的接枝为金属纳米颗粒的沉积提供了大量的锚定位点,有助于金属纳米颗粒在其上的分散。Pd/GO-PNIPAM在高温下（80℃）肉桂醛（CAL）的选择性加氢反应中显示出优良的催化性能,初始转换频率（initial TOF）达192.3min^-1,高于GO负载Pd催化剂（Pd/GO,103.5min^-1）。Pd/GO-PNIPAM较高的Pd纳米颗粒分散性和高温下对CAL良好的吸附性能协同作用,导致其催化活性提高。     

氮化碳负载钯催化剂催化苯酚加氢制环己酮

为了开发苯酚加氢制环己酮高效催化剂,将脲在550 ℃高温聚合,制备了片层状氮化碳催化剂载体g-CN;负载钯纳米粒子后,得到Pd/g-CN催化剂。采用红外光谱、X射线粉末衍射、透射电镜和X射线光电子能谱对催化剂进行表征。将Pd/g-CN催化剂用于催化苯酚水相加氢,考察了不同载体和反应温度对催化性能的影响,并对催化剂重复使用性能进行研究。结果表明,载体g-CN含有大量的含N基团,能有效稳定金属纳米粒子,从而获得粒径较小、分散较好的Pd纳米粒子;同时,g-CN具有较强碱性,有利于苯酚的吸附,可提高苯酚的反应速率和环己酮选择性。采用负载Pd质量分数2%的Pd/g-CN催化剂,在反应温度80 ℃、反应压力0.1 MPa、n(Pd)∶n(苯酚)=0.02、苯酚1 mmol、水3 mL和反应时间3 h条件下,苯酚可完全转化,环己酮选择性高达99%。Pd/g-CN催化剂制备工艺简单,原料价廉,催化性能优异。     

Ag/rGO纳米粒子的合成及其催化还原对硝基苯酚

采用液相共还原法在没有表面活性剂条件下原位制备Ag/rGO纳米催化材料,并用XRD、EDX、FTIR、Raman、SEM和TEM对所得产物进行了详细表征。结果表明:氧化石墨烯和银离子同时被还原,直径约为5nm的银纳米粒子均匀负载在石墨烯片层上。所制备的Ag/rGO纳米催化剂对硼氢化钠还原对硝基苯酚(4-NP)具有明显的催化活性;当Ag负载量(质量分数)为10%时,该反应在室温下的反应速率常数可达到0.332min-1,表观活化能为34.4kJ·mol-1。该Ag/rGO纳米复合粒子有望成为还原对硝基苯酚的工业催化剂。     

氧化石墨烯掺杂锌铝类水滑石负载钯金催化剂的制备及催化性能

采用离子交换-还原法制备了氧化石墨烯(GO)掺杂锌铝类水滑石负载钯金双金属纳米颗粒的催化剂(Pd Au/Zn-Al LDHs/GO),通过XRD、TEM表征了催化剂的结构,以GO掺杂锌铝类水滑石为载体负载钯金纳米颗粒粒径小(约2nm)且分散均匀。以苯甲醇空气氧化形成苯甲醛的反应为模型,评价催化剂的催化性能,探讨了载体及钯、金比例对催化反应的影响。催化结果表明,氧化石墨烯掺杂的锌铝类水滑石是考察载体中最好的钯、金催化剂的载体,随着钯金比的增加催化剂的催化活性先增加后降低,生成苯甲醛的选择性下降,当钯金比例为1∶1时,催化剂(Pd1Au1/Zn-Al LDHs/GO)的综合催化性能最好,催化活性随反应温度的升高而升高,但选择性随温度的升高而下降。在Pd1Au1/Zn-Al LDHs/GO催化下,80℃反应8h后苯甲醇的转化率可达96%,苯甲醛的选择性为93%,催化剂循环使用4次后仍保持较好的催化性能。     

Pd-Fe/TiO2常压催化加氢制备3-氯-4-氟苯胺的研究

研究了以Pd-Fe/TiO2作催化剂,3-氯-4-氟硝基苯常压加氢制备3-氯-4-氟苯胺的方法,考察了该催化剂对3-氯-4-氟硝基苯的常压加氢反应的性能,探讨了影响加氢反应的主要因素。实验表明,经KBH4处理过的催化剂具有较高的催化活性,Fe的引入同时提高了催化剂的催化活性和选择性。当催化剂中Pd的质量分数为5%,Fe的质量分数为0.2%,催化剂用量为13.2×10-3g Pd/0.1 mol硝基物,溶剂用量为80 mL无水乙醇/0.1 mol硝基物,反应温度50℃时,3-氯-4-氟苯胺的产率为98.0%,纯度达99.0%以上。     

Pd/Co_3O_4金属催化剂的制备及其催化还原邻氯硝基苯的研究

采用浸渍法制备了Pd/Co_3O_4负载型金属催化剂,进一步考察了其催化邻氯硝基苯加氢反应的催化性能。研究表明:以纳米Co_3O_4为载体所制得的Pd/Co_3O_4金属催化剂用于邻氯硝基苯催化加氢反应具有较高的反应活性和选择性,反应转化率达85%以上,其中邻氯苯胺的选择性也达到90%以上。     

凹凸棒土负载Pt催化剂的氯代硝基苯选择性加氢性能

以3 mol·L-1的HCl酸化凹凸棒土为载体,200℃还原制备负载型纳米Pt催化剂,并应用于氯代硝基苯选择加氢反应。在反应温度60℃和反应压力2.0 MPa条件下,催化剂显示出优异的加氢活性和选择性,在氯代硝基苯完全转化情况下,氯代苯胺选择性达100%,制备的催化剂具有很高的金属分散度,Pt纳米粒子粒径约2 nm,凹凸棒土载体对提高Pt分散度发挥了关键的作用,高分散纳米Pt粒子显著提高催化剂的加氢活性与氯代苯胺选择性,完全抑制了脱氯现象。     

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。