乙烯酮氯化法合成氯乙酰氯

以乙烯酮和氯气为原料在溶剂中反应合成了氯乙酰氯,适宜溶剂为磷酸三乙酯,采用带夹套的填料塔式反应器。在最佳工艺条件：溶剂比（溶剂与反应生成产物的质量之比）约１－０,反应温度２０ ～３０ ℃,反应压力约９－３ ｋＰａ,原料配比ｎ（Ｃｌ２）∶ｎ（ＣＨ２ＣＯ） ＝（１－０５～１－２０）∶１ 下,氯乙酰氯收率达９２－５ ％ 以上,纯度可达９８－５％ 以上。     

甲苯非催化氯化制备邻氯甲苯

通过甲苯的非催化环氯化方法,可以明显提高产物中邻氯甲苯质量含量。合适的反应条件为：温度 ３０３ Ｋ,通氯速率４．６×１０－ ２ ｓ－ １ ,溶剂与甲苯的体积比为２。与传统的 Ｆｅ Ｃｌ３ 催化氯化相比,邻氯甲苯与对氯甲苯质量比从１．１提高到２．３６,本流程中使用自产盐酸作氯化溶剂,氯化液分离容易,省去了水洗,没有废水排放,避免了精馏设备腐蚀。     

氯化棉油酸甲酯的研究

棉油酸经氯化－酯化－蒸馏制得氯化棉油酸甲酯。采用正交实验法筛选出了此工艺的最佳工艺条件。棉油酸氯化最佳工艺条件：反应时间为３．５ｈ，催化剂用量为棉油酸重量的０．３％，反应温度为７０℃，通氯量（氯气与棉油酸的摩尔比）为２０：１。氯化棉油酸甲酯化最佳工艺条件：反应温度为１８０℃，催化剂用量为氯化棉油酸质量的２％，甲醉：氯化棉油酸＝１：２．０（ｍｏｌ），反应时间为４ｈ。在此条件下进行平行试验，精酯收率均在８０％以上。     

聚（2,5—二甲基）对苯硫醚合成的初步研究

介绍以硫磺、氯和对二甲苯为原料,无水三氯化铁（ＦｅＣｌ３）作催化剂,三氯甲烷（ＣＨ３Ｃｌ３）作溶剂,合成聚（２,５－二甲基）对苯硫醚（ＤＭＰＰＳ）。最佳反应条件为：最佳投料摩尔比：对二甲苯／ＳＣｌ２／ＦｅＣｌ３＝１．０／１．０２／０．１０,反应温度２０～８０℃,反应时间５～６ｈ。收率为６２．５％。产品经红外光谱、Ｘ射线衍射光谱、激光拉曼光谱和差热分析验证,为线型结晶性,无双硫键,熔点Ｔｍ为３０６℃（美国ＲｙｔｏｎＶ－１型ＰＰＳ熔点为２７５～２８５℃的工程高聚物。所述合成方法原料和催化剂价廉易得、合成工艺简化、无副产物ＮａＣｌ产生、操作易、周期短、成本比ＰＰＳ低。其不足之处是产品收率不够高,有待在溶剂和催化剂选择方面作进一步研究。     

铜铬废合金的腐蚀分离

１实验１．１实验用品：Ｃｕ－Ｃｒ废屑由锦州华光厂提供，铬含量５７．２％。试剂：工业级盐酸、氨水、ＮＨ４Ｃｌ、ＣｕＣｌ２１．２实验步骤：称取１００ｇＣｕ－Ｃｒ合金屑，废屑厚度＜０．５ｍｍ，较大的废料砂磨成粉末，置于尼龙纱网中，悬挂于１０００ｍＬ大烧杯中...     

用相转移催化合成4—烷基苯甲酸

以烷基苯乙酮为原料，工业废氯气的回收碱液次氯酸钠溶液为氧化剂，在相转移钠化剂聚乙烯醇（ＰＥＧ）作用下，合成了４－烷基苯甲酸Ｒ＝ＣＨ３，ＣＨ３（ＣＨ２）ｎ，ｎ＝１￣４）。优选出最佳工艺条件：ｎ（次氯酸钠）：ｎ（烷基苯乙酮）为４．０：１．０，反应混合液ｐＨ≥１３，相对１ｍｏｌ烷基苯乙酮ＰＥＧ－４００用量为２００ｍＬ，烷基苯甲酸收率大于９０％，质量分类大于９５％。     

对氯甲苯氯化制2,4-二氯甲苯

用正交试验法研究了由对氯甲苯经催化氯化制取２，４－二氯甲苯的最佳反应条件。反应温度３３３Ｋ，催化剂《ＳｂＣｌ＿３）用量１．５％时，对氯甲苯转化率为５９．７％，２，４－二氯甲苯的收率为４５．１３％。     

宇佐美曲霉酸性蛋白酶发酵工艺研究

宇佐美曲霉Ｌ３３５是一株分泌高单位酸性蛋白酶的产生菌,本研究采用单因素搜索和正交试验,通过摇瓶发酵和２Ｌ搅拌罐发酵,对其发酵工艺进行优化。结果表明,较适宜的发酵培养基（ｇ／１００ｍＬ）为黄豆粉５．０、玉米粉１．２、鱼粉０．８、ＣａＣｌ２ ０．５、Ｎａ２ＨＰＯ４ ０．２、ＮＨ４Ｃｌ１．０、蚕蛹水解液１０．０;通气量控制２５ｈ前为１：０．４ｖ／ｖ／ｍ、２５－５０ｈ１：１．０ｖ／ｖ／ｍ,５０ｈ后１：３ｖ     

溶剂法制取硫酸钾连续化新工艺的研究

提出了以工业硫酸、工业氯化钾为原料制取Ｋ２ＳＯ４的溶剂法连续化新工艺，其较佳工 条件为：原料配比Ｈ２ＳＯ４：ＫＣｌ：Ｓ′＝１．０：２．０：２．１，反应温度５０℃，反应时间２０ｍｉｎ。该工艺产品纯度好，转化率达９８％以上，生产效率高，适用于工业化生产。     

用电势法测定混合电解质溶液中各个组分的活度系数

本文用无液接电势电池：Ｎａ－ＩＳＥ（或Ｋ－ＩＳＥ）｜（ＮａＣｌ（ｍＡ），ＫＣｌ（ｍＢ），Ｈ２Ｏ｜Ｃｌ－ＩＳＥ同时测定了２９８．１５Ｋ，溶液离子强度Ｉ：０．１、０．５、１．０、１．５、２．０和２．５ｍｏｌ／ｋｇ时，钠电极与氯电极组成的电池和钾电极与氯电极组成的电池的可逆电势值，根据Ｎｅｒｎｓｔ方程分别求出ＮａＣｌ－ＫＣｌ－Ｈ２Ｏ体系中，ＮａＣｌ和ＫＣｌ的平均活度系数。用Ｐｉｔｚｅｒ方程拟合两套实验数据，求出两套基本一致的Ｐｉｔｚｅｒ混合参数θＮａ－Ｋ和。将混合参数代回Ｐｉｔｚｅｒ方程，分别求出另一组分的平均活度系数，计算值与实验值比较，标准偏差分别为：０．００８１（ＮａＣｌ）和０．００７３（ＫＣｌ）。     

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.