β-异佛尔酮异构成α-异佛尔酮的化学平衡和动力学的研究

本文研究了β-异佛尔酮在423.15-463.15K 异构化成α-异佛尔酮的化学平衡和反应动力学。结果表明,这一反应是放热的一级可逆反应。其化学平衡常数与温度的关系为:lnK=2885/T-8.684;反应热为:H~0=-23.99kj/mol;反应速率常数为:lnk_1=-9008.57/T 15.06;lnk_(-1)=-11088.98/T 15.05;活化能为:Ea,1=71.90kj/mol;E_(a,-1)=91.19kj/mol。     

氯亚乙基肼基甲酸乙酯生成反应热动力学研究

利用微量热量计测定了氯乙醛和肼基甲酸乙酯在水溶液中(298.15K)生成氯亚乙基肼基甲酸乙酯的反应焓变为(-13.035±0.088)kJ/mol。计算得出该反应的热动力学参数:反应级数n=1;速率常数k=2.018×10-3s-1及反应活化自由能ΔG ≠=88.408kJ/mol。结果表明,该反应在室温下易于进行。     

制备双羟基四配位硅反应速率常数的测定

探讨了用电导法跟踪高反应活性的五配位硅钾化合物与2-氯乙醇反应制备双羟基四配位硅化合物的动力学行为,从而确定该反应的反应级数为二级反应,得出在甲醇体系中反应的速率常=1.233h、t53℃=数k64℃=1.818(mol/dm3)-1·h-1、k53℃=0.4437(mol/dm3)-1·h-1,半衰期t64℃11225.051h,和该反应的活化能Ea=86.987kJ/mol。     

脲衍生物对环氧树脂/双氰胺体系促进作用的研究

对比了不同结构的脲衍生物[3-(3-氯-4-甲基苯基)-1,1-二甲基脲(A)、3-(3,4-二氯苯基)-1,1-二甲基脲(B)、3-(4-氯苯基)-1,1-二甲基脲(C) ]对环氧树脂/双氰胺体系的促进作用。利用差示扫描量热仪和傅里叶变换红外光谱研究了3种环氧树脂/双氰胺/脲体系的反应活性和固化反应动力学。结果表明,体系A的最佳配比为：环氧：双氰胺：脲A=100：6：4（质量比,下同）,130 ℃时40 min就可以完全固化,其表观活化能（Ea）=64.66 kJ/mol,反应级数（n）=0.897;体系B的Ea=71.68 kJ/mol,n=0.930;体系C的Ea=71.03 kJ/mol,n=0.928;3种体系配制的胶液的室温剪切强度均大于20 MPa,体系A的粘接强度达到24.98 MPa。     

用DSC法研究聚苯乙烯磺酸钠阳离子交换树脂热分解反应的非等温动力学

用DSC法研究了粉状聚苯乙烯磺酸钠阳离子交换树脂受热反应的非等温动力学。在温度区间为390~500℃,先发生一个放热反应,其后是吸热反应。测定了这两个表观受热反应的动力学基础数据-表观活化能和频率因子分别为:(2.8±0.4)×102kJ/mol,278±17 kJ/mol和(2.4±0.4)×1020/min,(5.2±0.4)×1019/min(99%置信度)。还测定了上述两个表观反应的反应热,前者为-8±3 J/g,后者为77±8 J/g(390℃时无水树脂重)(95%置信度)。     

关于氟化氢铵与硅反应的动力学研究

介绍了白炭黑和废砂浆的研究现状,阐述了硅制取白炭黑的两反应两循环新的氟化法工艺路线。利用传统的排水收集气体的方法,并将气体量转化为浓度,研究了氟化氢铵与线切割废砂浆中硅反应的动力学。结果表明,该反应符合二级反应规律[-r=k(C(NH4)HF2)2],确定50℃与60℃条件下的反应速率常数:k50=3.47×10-4mol3/(L.s)和k60=5.62×10-4mol3/(L.s),以及此反应的活化能Ea=43.16 kJ/mol与指前因子A=3 288.85。     

大庆某低渗轻质油藏注空气低温氧化反应动力学研究

轻质油藏注空气提高采收率的机理之一是在油藏中发生低温氧化反应,低温氧化反应进行的程度将对油藏注空气开发的可行性产生决定性的影响。通过在RUSKA2370-601PVT筒中进行的大庆某低渗油田原油与空气恒温恒压氧化反应实验数据,获得轻质油藏注空气低温氧化反应动力学参数为:原油氧化反应为零级反应;21 MPa,87℃时氧化反应的速度常数KO2为1.2255×10-4mol/(mL.h),21 MPa,127℃时氧化反应的速度常数KO2为7.0101×10-4mol/(mL.h),原油样品的阿仑尼乌斯活化能Ea为52.1 kJ/mol。     

双酶协同水解微波改性木薯淀粉的动力学研究

研究了α 淀粉酶和葡萄糖苷酶协同水解微波改性木薯淀粉的动力学,在单一水解体系中,α 淀粉酶和葡萄糖苷酶对微波改性淀粉颗粒的降解遵循Michaelis Menten方程,葡萄糖苷酶的米氏常数Km=18 718mol/mL,最大反应初速度Vmax=0 745mol/(mL·min),α 淀粉酶的米氏常数Km=88 334mol/mL,最大反应初速度Vmax=1 039mol/(mL·min)。葡萄糖对反应体系具有竞争性抑制剂的作用,其抑制常数Ki=9 656×10-4mol/mL。双酶协同作用的水解效率比单酶作用的水解效率高。     

负载钛催化丁二烯-异戊二烯共聚合反应动力学的研究

研究了TiCl4 /MgCl2 负载型高效催化剂催化丁二烯 -异戊二烯共聚合的动力学特征 ,并对影响聚合速率的因素进行了考察。首先通过计算排除了扩散控制对反应总聚合速率的影响 ,测定了单体浓度和催化剂浓度的反应级数和表观活化能 (2 2 .8kJ/mol) ,建立的聚合速率方程为 :R =kp·f·[Ti]·[M]。     

Guerbet十四醇的合成与表征

以正庚醇为原料 ,通过Guerbet反应合成Guerbet十四醇 (2 戊基壬醇 ,C14 GA)。用IR、NMR和元素分析测定了C14 GA的结构 ,并研究了反应温度和用料比对其产率的影响。实验结果如下 :(1)在较优化的反应条件下 (正庚醇的总加入量为 1mol,在实验过程中 ,先加入 1/ 3mol庚醇和 1/ 4mol的KOH ,在 16 0℃下反应 2h ,然后再加入剩下的 2 / 3mol庚醇和 4g 5 %Pd -C催化剂 ,在 15 5℃下反应 6h)合成产物 ,其产率可达到 5 4 2 0 % ;(2 )所合成的产物与试图要得到的Guerbet十四醇 (2 戊基壬醇 ,C14 GA)含有相同的基团 (2×—CH3、10×—CH2 —、1×CH、1×—CH2 —O—和 1×—OH) ,而且 ,所合成的产物中 ,w (C) =79 0 6 % ,w (H ) =13 6 2 % ,与从Guerbet十四醇分子式计算的理论值w(C) =78 5 0 % ,w (H) =14 0 1%基本一致。可见所合成的产物正是Guerbet十四醇 (C14 GA)     

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。