介孔分子筛MCM-41—SO3H 催化木糖脱水制备糠醛的研究

采用在MCM-41分子筛上先嫁接—SH,再经氧化和酸化的方法制备了介孔分子筛固体酸催化剂MCM-41—SO3H,对催化剂进行了表征,并对其用于木糖脱水环化生成糠醛的反应进行了研究。当木糖与催化剂的质量比为0.8、反应温度为170 ℃、反应时间为4 h时,木糖的转化率为83.4%,生成糠醛的选择性为76.7%,糠醛收率为64.0%。该催化剂的优点是糠醛收率高于硫酸作催化剂时的收率;不产生酸性废水;催化剂经再生处理后能重复使用,但糠醛收率降为39.7%。     

MCM-41分子筛催化木糖制备糠醛的研究

以MCM-41分子筛为催化剂,在正丁醇与水构成的两相溶剂体系中,将木糖脱水转化为糠醛。考察了两相溶剂体系中正丁醇与水的体积比、反应温度、反应时间以及MCM-41催化剂循环使用次数对木糖转化率和糠醛收率的影响。实验结果表明:在木糖浓度为10%、催化剂用量为50%(以木糖用量计),正丁醇与水体积比率为1:1,反应温度为170℃时,反应4 h后木糖转化率可达到96.8%,而糠醛收率最高可达44.05%。同时,研究表明,在其它反应条件相同的情况下,加入10%(以木糖用量计)的NaCl可显著提高糠醛收率,增幅可达23.1%。     

氯化铁/氯化钠催化木糖反应萃取过程优化

为解决糠醛生产过程中收率低和污染严重等问题,提出使用氯化铁/氯化钠复合催化木糖经反应萃取生产糠醛的新工艺。首先研究了催化剂用量对反应过程的影响,得到了最优的催化剂添加量。然后以获得降解过程中较高的木糖转化率和糠醛收率为目的,通过响应曲面法研究了反应温度(170—210℃)、溶剂比(体积比1—5)、反应时间(15—75 min)对木糖降解过程的影响,并建立了木糖转化率和糠醛收率的二次多项式模型。由响应面分析和方程模型优化可以得到木糖降解过程的最优降解条件:反应温度190℃,溶剂比4,反应时间48 min,此时木糖转化率为93.1%,糠醛收率为75.6%。在最优降解条件下的实验验证结果与模型预测值非常接近,说明模型是适用的。     

氯化铁催化木糖降解制备糠醛反应动力学

研究了温度在443.15～483.15K时0.1mol/L氯化铁催化木糖降解生成糠醛的反应动力学过程。首先建立并验证了反应的动力学模型,根据模型得到了木糖降解、糠醛降解和缩合反应的速率常数。由阿伦尼乌斯方程拟合得到其表观活化能分别为107.94kJ/mol、65.86 kJ/mol和26.36kJ/mol。结果表明,高温和较短反应时间有利于糠醛收率的提高,在反应温度483.15K、60min条件下,最大糠醛收率可达78%。     

糠醛生产新工艺的研究

提出了糠醛生产新工艺并得出了新工艺的最佳工艺参数。新的糠醛生产工艺是用汽爆法取代酸性水解处理玉米秸秆、经水提制得含木糖的水提液、木糖脱水环化生成糠醛,在脱水环化时使用超临界CO2(SC-CO2)流体作萃取剂。最佳的工艺参数是汽爆压力1.4 MPa、维压时间为4min;木糖脱水环化生成糠醛时反应温度180℃,反应时间180min,SC-CO2流量1.0×10-4 kg/s,反应压力16MPa,糠醛得率可达63.0%。采用新工艺,糠醛质量收率为1.2%,并能大幅减少三废的数量。     

微波辐照木糖降解制备糠醛反应动力学

以硫酸为催化剂,考察了微波辐射条件下,反应温度和硫酸浓度对木糖降解反应的影响,拟合实验数据并建立反应动力学方程。结果表明,木糖转化率随温度的升高而增加,随着硫酸质量分数的增加而增加,催化活性较好。木糖脱水反应级数为一级,降解反应的活化能为48.05 kJ/mol,指前因子与硫酸浓度成幂指数关系。通过实验数据拟合得到的动力学方程能较好的反映实际木糖降解反应。     

碳基固体酸催化D-木糖选择性转化合成糠醛的研究

采用固体酸催化D-木糖脱水制备糠醛具有经济价值高、易分离和环境友好等优点;本文中,主要研究了碳基固体酸在木糖脱水中的催化性能,所用的固体酸包括木质素磺酸聚合物催化剂（LF-A, LF-B, LF-C, LF-D）和磺化碳材料FS等;其中,木质素磺酸聚合物催化剂是借助酚醛缩合过程将木质素磺酸盐和醛类反应制得;磺化碳材料则是采用水热合成法以糠醛、十二烷基苯磺酸钠为原料制备;通过对催化剂种类、反应媒介、时间、催化剂用量及反应温度等条件的详细研究,发现LF-A催化剂的效果较好,当原料D-木糖为1.0 g,反应温度为170 ºC,反应时间4 h,催化剂用量为0.08 g,溶剂为γ-丁内酯时,糠醛的收率可达72.9%;同时,对固体酸催化剂进行XRD,FT-IR,TG-DTG,SEM和TEM等表征,并找出了催化剂结构与活性之间的相互关系.     

高温液态水条件下木糖直接转化制备糠醛的工艺

使用自制的高温高压反应釜,在高温液态水（HTW）的条件下对木糖直接转化制备糠醛的过程进行了研究。考察了HTW作为反应介质对木糖转化率和糠醛产率的影响,并与文献中所采用催化剂的催化效果进行了对比,探索了不同的溶剂对反应产物中糠醛的萃取效果。研究结果表明：HTW作为反应介质对木糖直接转化制备糠醛具有优良的反应性能,可以替代液体酸和固体酸作用于木糖制糠醛,在优化的工艺条件下,当木糖初始浓度为10%（g/g）、反应温度为200 ℃、反应时间为3 h时,糠醛的产率高达78%。此外,乙酸丁酯作为萃取剂对于糠醛的萃取具有良好的萃取效率。所得结果为工业化生产糠醛奠定了实验基础和理论依据。     

固体酸催化果糖制备5-羟甲基糠醛的研究

研究了以二甲基亚砜为溶剂、TiO_2-SiO_2为催化剂催化果糖脱水生成5-羟甲基糠醛(HMP)的反应,分别考察了不同摩尔比TiO_2-SiO_2催化剂、反应时间、催化剂用量、果糖添加量等工艺参数对果糖脱水制备HMF催化活性的影响.在TiO_2-SiO_2作为催化剂、150℃和反应3 h的条件下,5-羟甲基糠醛的收率可达83.8%.     

铬形态及使用条件对糠醛催化加氢反应产物分布的影响

采用共沉淀法制备系列Cu-Cr糠醛加氢催化剂,考察不同铬形态对催化剂反应性能的影响。采用管式连续流动固定床积分反应器, 研究糠醛在Cu-Cr催化剂上的气-液相加氢反应规律。结果表明,制备催化剂时的铬原料不同,将极大地影响催化剂的加氢活性和产物选择性,以硝酸铬形式加入制备的催化剂对糠醇的生成较为有利,而以醋酸铬形式加入制备的催化剂对甲基呋喃的形成有利;在(70～110) ℃,随着温度升高,糠醛转化率和糠醇选择性增加,2-甲基呋喃选择性降低;糠醛流速为(0.01～0.06) mL·min^-1时,随着流速的增加,糠醛转化率下降,0.03 mL·min^-1时糠醇选择性出现极大值,而副产物2-甲基呋喃和呋喃类则在此处出现极小值。副产物戊二醇和四氢康醇的选择性则随着糠醛流速的增大上升。     

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。