合成己二腈宏观反应动力学的研究

本文对于以磷酸为催化剂,用熔融(液相)已二酸与气相氨作用生成己二腈的反应过程,研究了中和与脱水反应的宏观动力学。实验考察了温度、时间和催化剂浓度等对反应的影响,结果表明中和反应是受传质和化学反应动力学共同影响的快速反应。在 C_B≥3.5%时,反应对己二酸浓度为一级,在 C_B<3.5%时,属于动力学控制的二级反应,其速率常数为:k_1=3.31×10~4exp[-(13.8-158C_P)×10~3/RT]k_2=3.07×10~4exp[-(23.4-420C_P)×10~3/RT]同时提出了总脱水为一级反应,其速率常数为:k=1.03×10~8exp{-[23.6+2.07exp(-644C_P)]×10~3/RT}     

异戊二烯在二氧六环中的负离子聚合动力学

研究了以正丁基锂为引发剂 ,异戊二烯在二氧六环溶剂中负离子聚合的动力学。结果表明 ,增长反应对单体浓度和引发剂浓度皆为一级反应 ,活化能为45.22kJ/mol,频率因子为4.832×108L/(mol·min) ,并求出了生成1,4 -结构、1,2 -结构和3,4 -结构产物的速率常数分别为2.77×1012exp( -74760/RT) ,9.82×106exp( -39190/RT) ,8.02×107exp( -41180/RT)。     

活性炭催化剂上甲基叔丁基醚裂解反应动力学的研究

常压下,在265～295℃温度范围内,用内循环无梯度反应器对甲基叔丁基醚(MTBE)在CRN型活性炭催化剂上裂解制异丁烯的反应动力学进行了研究。研究结果表明,裂解反应由吸附的MTBE生成非吸附产物的不可逆表面反应所控制,其本征动力学方程为 (-r_A)=κP_A/(1+κ_AP_A)式中κ=2.6167×10~9 exp(-1.4730×10~2/RT) κ_A=8.6829×10~6 exp(-1.1661×10~2/RT)     

桑根酮C、D在碱液中的稳定性研究

本文分别研究了桑根酮C、D在NaOH和Na_2 CO_3 水溶液中的稳定性 ,得到了桑根酮C、D在NaOH水溶液中的降解速率分别为dC/dt=1.30 8× 10 11exp(- 7770 2 .8/RT)CC1.40 1NaOH和dC/dt=5 .75 1× 10 11exp(- 830 37.4 /RT)CC1.40 0NaOH,桑根酮C、D在Na2 CO3 水溶液中的降解速率分别为dC/dt=1.4 14× 10 15exp(- 10 2 918.5 /RT)CC0 .2 955Na_2 CO_3,dC/dt=6 .16 3× 10 14exp(- 10 195 1.3/RT)CC0 .3 0 81Na_2 CO_3。 2 5℃时 ,30min以内 ,桑根酮C、D在 2 .0 %的Na_2 CO_3 水溶液和 0 .5 %NaOH水溶液中的降解率均低于 5 .0 %。这为碱液法从桑白皮中提取桑根酮的工艺过程的开发及工艺参数的设定提供了理论依据。     

快速流化床反应器用于丁烯氧化脱氢制取丁二烯的宏观动力学研究

本工作是在内径为26mm 的快速流化床反应器中,以丁烯氧化脱氢制取丁二烯的过程为内容,在330℃～370℃的温度范围内进行了宏观动力学研究。根据快速流化床的流动特性,以气相为基础,对其实验结果采用了拟均相模型处理,求得总反应转化率表达式 X_A=1-exp(-kτ),其中反应速度常数 K=1.123×10~4exp[-42990.70/RT],总的反应表观活化能 E=4.299×10~4(J/mol).同时还计算了主付反应的下列参数:k_1=1.133×10~4exp[-4.339×10~4/RT]k_2=2.511×10~2exp[-3.739×10~4/RT]E_1=4.339×10~4 J/molE_2=3.739×10~4 J/mol并以下列方程组:k_1,k_2x_A=1-exp[-(k_1+k_2)ετ]y_Q=(k_1/k_1+k_2)·X_A来予测反应过程中丁烯的转化率及丁二烯的收率情况,用此方法计算的结果与实验值之相对误差均在±8%范围以内。     

铯-铷-钒系低温硫酸催化剂上SO_2氧化反应速率的机理解释

以碱金属盐为助催化剂的铯 -铷 -钒系硫酸催化剂 ,在 380～ 5 2 0℃下 SO2 氧化反应机理为三步催化反应 ,并推导出其动力学机理模型 :r=k1P1/ 2O2k2 +k3 PSO3 +PSO3 PSO2(1- PSO3 PSO2 P1/ 2O2 KP)。采用内循环无梯度反应器测定了SO2 氧化反应动力学数据 ,并利用 Powell法对动力学模型进行参数估值 ,得到 :k1=0 .15 2 exp(- 6 2 0 73/ RT) ,k2 =8.18exp(- 2 384/ RT) ,k3 =0 .2 2 1exp(- 18949/ RT)。方差分析表明 ,在显著性水平 0 .0 1下 ,三步反应机理模型对反应速率实验值拟合较好 ,标准偏差为 0 .2 42     

一乙醇胺催化脱氢合成氨基乙酸钠反应动力学研究

探讨了以雷尼 (Raney) Cu为催化剂由一乙醇胺催化合成氨基乙酸钠反应的机理 ,推导了合成过程的动力学方程。实验结果表明 :该反应服从一级反应动力学规律 ,其反应速率方程为 r=kc A。根据线性化的Arrhenius方程拟合得到该反应的反应速率常数 k=6 .8111× 10 15exp(- 147.80× 10 3/ RT)。用所建立的动力学模型预测其他温度下的反应转化率 ,计算值与实验值比较平均误差小于 1.2 5 %。     

铯—铷—钒系低温硫酸催化剂上SO2氧化反应速率的机理解释

以碱金属盐为助催化剂的铯－铷－钒系硫催化剂，在380－520℃下SO2氧化反应机理为三步催化反应，并推导出其动力机理模型：r=(k1P^1/2o2)/(k2 k3Pso3 Pso3/Pso2)(1-Pso3/Pso2P^1/2o2Kp)。采用内循环无梯度反应器测定了SO2氧化反应动力学数据，并利用Powell法对动力学模型进行参数估算，得到：k1=0.152exp(=62073/RT),k2=8.18exp(-2384/RT),k3=0.221exp(-18949/RT)。方差分别表明，在显著性水平0．01下，三步反应机理模型对反应速率实验值拟合较好，标准偏差为0．242。     

吡啶为助剂合成甲酸甲酯的动力学研究

在60～90℃对以吡啶为助催化剂由一氧化碳合成甲酸甲酯的反应进行了动力学研究。结果表明该反应为2级反应,速率方程rυ=-dpco/dt=k[MOH]pco,无助催化剂时反应活化能Ea=67.63kJ/mol,反应速率常数k=9.66×106exp(-67.63×103/RT)(mol-1·L·min-1);当有助催化剂存在时,反应活化能为Ea=61.19kJ/mol,反应速率常数k=8.82×106exp(-61.19×103/RT)(mol-1·L·min-1)。并对助催化剂吡啶的助催化机理进行了探讨。     

硫化氢对铁铬钼催化剂一氧化碳变换动力学行为的影响

在玻璃反应器中,以混有不同浓度(0、450、850ppm)硫化氢的工业半水煤气研究了B112型铁铬钼变换催化剂的动力学行为,接二级反应速率方程对试验数据进行处理,其反应速率常数分别为: H_2S=0时:k_T=3.797×10~5exp(-66573/R_gT); H_2S=450ppm时:k_T=2.116×10~4exp(-57923/R_gT); H_2S=850ppm时:k_T=1.637×10~4exp(-58731/R_gT);     

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。