间歇减压精馏分离2-甲基吡啶/2-羟乙基吡啶

采用间歇减压精馏法实现了2-甲基吡啶和2-羟乙基吡啶这一热敏性混合物的分离,并考察了投料组成与操作压力对减压精馏过程的影响。结果表明,高真空条件降低了塔釜温度从而避免了物料在塔釜中受热变性,对于热敏物料2-羟乙基吡啶,减压精馏过程中压力应控制在4325 Pa以下,此时塔釜产品2-羟乙基吡啶的质量分数均能大于97%,同时收率能保持在86%以上。在压力为1325 Pa时,不同投料组成下塔顶产品2-甲基吡啶的质量分数和塔釜产品2-羟乙基吡啶的质量分数均高于98%,两者的收率也均在85%以上,能够很好地满足工业生产要求。     

真空间歇精馏法分离紫罗兰酮异构体

采用真空间歇精馏法实现了α-紫罗兰酮和β-紫罗兰酮异构体混合物的分离,考察了原料液组成、回流比、塔顶采出率、塔釜加热温度、塔节保温温度对异构体分离的影响,同时探讨了精馏操作时间对产品质量的影响。结果表明,在适宜的精馏操作条件下,塔釜产品β-紫罗兰酮的质量分数高于96%,同时收率能保持在90%以上,满足医药中间体应用要求。     

塔釜回流共沸精馏技术的研究

通过-个具有塔釜回流的精馏塔实验装置,以正己烷为共沸剂,从操作时间、回流比的控制、共沸剂的用量及实际应用等方面对塔釜回流共沸精馏技术分离乙醇-水共沸混合物进行了实验研究.研究结果表明:塔釜回流共沸精馏技术与常规共沸精馏技术相比,在其他操作参效相同,回流比大于3时,塔釜回流得到的产品纯度和收率有明显提高;达到同样的产品纯度和收率,塔釜回流所用的共沸剂量减少;但塔釜回流的操作时间延长.塔釜回流改善了常规的操作方式在生产应用上的不足.是一种很有应用前景的分离新技术.     

动态累积间歇精馏新操作方式研究

采用正丙醇-异丙醇混合物为分离物系,在动态累积间歇精馏理论基础上,提出了一种新的采用塔釜回流的操作方式,并在常规动态累积与精馏节能方面进行了对比。实验结果表明,在确保塔顶异丙醇产品纯度达到85%的条件下,节省了操作时间,进而可节约17%~33%的能耗,且收率提高1.5%~2.2%。     

带塔底储罐的间歇萃取精馏的实验研究

提出了带塔底储罐的间歇萃取精馏操作方式.新操作方式使精馏过程中加入的溶剂及塔内回流液直接流入塔底储罐,不再返回塔釜.以乙二醇为溶剂分离乙醇–水共沸物的实验研究表明,新操作方式克服了普通间歇萃取精馏塔釜体积庞大的缺陷,同时具有塔釜温度稳定、加热容易控制、收率提高等优点.     

真空间歇精馏法精制双环戊二烯的研究

采用真空间歇精馏技术精制聚酯级双环戊二烯中的双环戊二烯,考察了操作压力、回流比、塔釜和塔顶温度对双环戊二烯质量分数和收率的影响,优化得到较佳精馏操作条件.实验结果表明:适宜的工艺条件为塔顶压力9kPa,回流比为3,塔釜温度为68～106℃,塔顶温度为45～87℃,在以上条件下,产品中双环戊二烯质量分数达到96％以上,收率达到90％以上,为工业化提纯双环戊二烯提供了实验依据.     

减压间歇精馏制备δ-戊内酯新工艺的研究

以1,5-戊二醇为原料催化脱氢得到δ-戊内酯粗品,再采用减压间歇精馏工艺进行提纯,得到δ-戊内酯纯度为99. 8%、收率为95. 0%,产品质量达到了聚合级技术指标。减压间歇精馏工艺的操作条件为:压力5. 0 k Pa、塔顶温度140℃、回流比2. 5～3. 0。该新工艺能耗低、操作简便,工业化推广意义较大。     

真空精馏提纯对氨基三氟甲氧基苯的研究

采用真空间歇精馏技术对对氨基三氟甲氧基苯原料进行分离实验研究,考察了对氨基三氟甲氧基苯的热敏性;确定了安全的操作温度范围和适宜的操作策略。实验结果表明:采用变回流比操作,操作压力不超过5.0kPa,釜温低于140℃,产品中对氨基三氟甲氧基苯的质量浓度可达到99.5%以上,收率达到83.6%,其中各杂质的质量分数低于0.01%。     

真空间歇精馏提纯1,4-丁二醇生产残液

采用真空间歇精馏方法对从1,4丁二醇(BDO)生产残液中提取BDO的精制过程进行了研究.通过考察塔顶真空度、回流比和加热负荷等操作因素对分离效果的影响,确定了适宜的操作条件,塔顶压力为700 Pa,釜温在160～170℃之间,采用变回流比操作.结果显示,产品BDO的质量分数达到99.5％以上,收率80％以上.这种方法操...     

Research on distillation of heat-sensitive epoxycyclohexane

针对无溶剂法双氧水氧化环己烯合成环氧环己烷的油相反应液,采用常压精馏的方法对其进行了分离纯化,并得到了常压精馏操作的较佳工艺条件。在此工艺条件下,环氧环己烷的纯度和单程收率分别达到99.59%和85.87%,对常压精馏后的塔釜高沸点残留物进行减压精馏回收后,环氧环己烷总收率可以达90%以上,为其工业化生产提供重要的实验依据。     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

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.