2,6-萘二甲酸甲酯化反应工艺研究--催化剂的筛选及工艺条件的确定

研究２，６－萘二甲酸甲酯化反应过程，筛选出适宜的反应催化剂，并对钼酸铵为催化剂时的反应过程进行正交试验，确定最佳反应条件为反应温度１９０℃，催化剂用量１％，反应时间０．５ｈ，液固配比６：１，此条件下反应转化率可达９５．０３％。     

工艺条件对Al2O3·TiO2·ZnO·CuSO4／高岭土催化剂酯化性能的影响

进行了乙酸和正丁醇在Ａｌ２Ｏ３·ＴｉＯ２·ＺｎＯ·ＣｕＳＯ４／高岭土固体酸催化剂上合成乙酸正丁酯的气固相反应，试验了催化剂用量、醇／酸摩尔比、反应温度和反应时间等工艺条件对催化剂性能的影响，得到较佳的工艺条件为：催化剂用量０．９－１．０ｇ／ｍｏｌ乙酸，醇／酸摩尔比１．１－１．２，反应温度１３０℃－１４０℃和反应时间４－６ｈ。在此条件下酯化率９７％和选择性１００％。     

无毒增塑剂乙酰柠檬酸三丁酯的合成

用固体氯化物催化 民柠檬酸三丁酯,柠檬酸三丁酯和乙酸酐反应合成乙酰柠檬酸三丁酯。研究了催化剂用一、原料配比、反应温度、反应时间对合成反应的影响,确定了最佳工艺条件：（１）酯化反应：柠檬酸：正丁醇为１：３．５（ｍｏｌ）;反应温度为１３０℃;反应时间５ｈ,催化剂用量０．７％;（２）乙酰化反应：柠檬酸三丁酯：乙酸酐为１：１．６,反应温度为８５℃,反应时间为１ｈ,催化剂用量为０．０６％。酯化收率为９６．３     

聚乙二醇双硬脂酸酯的合成

采用亚磷酸与硫酸复合催化剂合成了聚乙二醇双硬脂酸酯，最佳工艺条件：ｎ酸：ｎ醇为２．８：１（ｍｏｌ：ｍｏｌ），复合催化剂用量为１．０％（以聚乙二醇计），反应温度１５０℃，反应时间５ｈ，真空度９７．３ｋＰａ。     

提高硝基甲烷产品收率的工艺优化

对合成硝基甲烷的工艺进行了研究，得到最佳工艺条件：硫酸二甲酯与亚硝酸钠物质的量之比为１：２，反应温度３０±２℃，反应时间４ｈ，催化剂用量７．０％，该条件下收率可达６９％，产品纯度≥９９．０％。     

由硫磺、氯气一步法制备二氯化硫

以工业硫磺和液氯为主要原料,一步法直接制备二氯化硫。确定了合成反应最佳工艺条件：起始反应温度１００～１１０℃,氯气通入时间（即反应时间）６ｈ,通氯气量７５Ｌ／ｈ,精制蒸馏温度６０～６５℃,稳定剂三氯化磷用量０．１％～０．３％。在此工艺条件下制备的二氯化硫收率可达８０％以上。     

甲基丙烯酸β—羟乙酯的合成研究

以十六烷基三甲氢氧化铵为催化剂和苯二酚为阻聚剂，由甲基丙烯酸甲酯和乙二醇合成了甲基丙烯酸β－羟乙酯，通过正交试验获得了最佳反应条件，反应温度１００℃～１１０℃，反应时间２．５ｈ，酯醇摩尔比１：１．５，催化剂用量为９．０ｍｌ，ＨＥＭＡ的产率为９２．３％。     

甲基丙烯酸β-羟乙酯的合成研究

以十六烷基三甲基氢氧化铵为催化剂和对苯二酚为阻聚剂，由甲基丙烯酸甲酯和乙二醇合成了甲基丙烯酸β－羟乙酯。通过正交实验获得了最佳反应条件：反应温度１００℃～１１０℃，反应时间２．５ｈ，酯醇摩尔比１∶１．５，催化剂用量为９．０ｍｌ。ＨＥＭＡ的产率为９２．３％。     

合成松香酸蔗糖酯的研究

松香酸甲酯化制备松香酸甲酯,再与蔗糖反应合成松香酸蔗糖酯。甲酯化最佳条件为松香酸∶甲醇＝１∶３（摩尔比）、时间１ｈ、温度７０℃、催化剂氢氧化钾用量２％,酯化率为９５．５％。松香酸蔗糖酯最佳合成条件为松香酸甲酯∶蔗糖＝１∶２（摩尔比）、时间３ｈ、温度９０℃、催化剂氢氧化钾用量３％,产物得率为９２．１％。产物有良好表面活性,其２％和４％水溶液的表面张力分别为３０．３３×１０－３Ｎ／ｍ和２７．５０×１０－３Ｎ／ｍ。     

2—甲基—2,4—戊二醇的合成

介绍了由二丙酮醇在高压，加热条件下还原合成２－甲基－２，４－戊二醇，影响２－甲基－２，４－戊二醇的收率的因素有：压力，温度，催化剂用量，反应时间及搅拌次数等，通过实验出如下最佳工艺条件，压力３．０ＭＰａ温度９５℃～１０５℃催化剂用量１０％，反应时间７ｈ，搅拌速率５５次／ｍｉｎ。     

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.