含氮杂环羧酸乙酯的微波合成

以异烟酸(烟酸)和无水乙醇为原料,浓硫酸为催化剂,在微波辐射下合成异烟酸(烟酸)乙酯,其结构通过红外光谱、质谱进行了确证。同时研究了醇酸物质的量比、催化剂用量及反应时间对酯化产率的影响,结果表明,醇酸物质的量比为8∶1,催化剂用量为8.0mL(0.15mol),反应时间为40min时,微波辐射功率为300 W的优化条件下,酯化产率最高,相应的产率为89.2%和95.0%。     

侧链携带二茂铁基的聚N-异丙基丙烯酰胺与β-环糊精聚合物构成的可控超分子体系的研究

采用侧链携带二茂铁基的聚N-异丙基丙烯酰胺〔poly(NIPAM/FCN)〕及β-环糊精聚合物〔poly(-βCD)〕构成超分子体系。以核磁共振氢谱、循环伏安、粒径分析等手段对poly(-βCD)与poly(NIPAM/FCN)之间的主客体包结作用的研究表明,二茂铁聚合物poly(NIPAM/FCN)可与poly(-βCD)形成氧化还原可控超分子体系,并且该体系的溶液性能可以通过氧化反应来调节。     

2-溴乙氧基苯的相转移催化合成研究

在四丁基溴化铵相转移催化剂存在下,以苯酚、1,2-二溴乙烷为原料合成2-溴乙氧基苯,分别研究了反应温度、反应时间、原料配比、催化剂用量等条件对合成反应的影响,确定了最佳工艺条件。该方法合成2-溴乙氧基苯的最佳工艺条件是:反应温度100°C;反应时间6 h;n(苯酚)∶n(1,2-二溴乙烷)=1∶1.15;n(苯酚)∶n(氢氧化钠)=1∶1.15;溶剂用量为40 mL(相对于0.15 mol苯酚),催化剂用量为1 g(相对于0.15 mol苯酚),2-溴乙氧基苯的收率可达到88.9%以上,产品纯度98.5%。     

Cope消除法合成N-异丙基丙烯酰胺

以丙烯酸甲酯和异丙胺为原料,二乙胺为保护剂,双氧水为氧化剂,经氧化胺Cope消除法合成了N-异丙基丙烯酰胺。用液相色谱法测定了3-二乙胺基-N-异丙基丙酰胺(DEAPAA)的氧化度及N-异丙基丙烯酰胺(NIPAM)的产率,考察了双氧水用量、催化剂和反应温度对氧化反应以及裂解温度、真空度和溶剂对裂解产物NIPAM收率的影响。结果表明,双氧水过量1倍,钨酸钠/焦磷酸钠为催化剂,于70℃氧化反应3 h,DEAPAA的氧化度几乎达到100%;在90℃、真空条件下氧化胺Cope消除制备NIPAM的产率可达70%⁷2%。     

Co~(3+)的电氧化合成及其在对甲砜基苯甲酸制备中的应用

以七水硫酸钴、浓硫酸、硫酸铵为原料,电氧化合成Co3+,用Co3+氧化对甲砜基甲苯合成对甲砜基苯甲酸。考察了电极材料、电解温度、电流密度、硫酸浓度以及电解液循环套用对电极反应和硫酸浓度、Co3+与对甲砜基甲苯物质的量比对氧化反应的影响。结果表明,在选用阳极二氧化铅、阴极铅为电极板,陶瓷膜作为阳离子交换膜,电解液浓度为c(Co2+)=0.5 mol/L、c (硫酸)=4.0 mol/L、c (硫酸铵)=0.15 mol/L,电极间距(d)为2 cm、电流密度(J)为350 A/m2、电解温度(T)为10℃时,电解液Co2+转化率可达80%,电解氧化电流效率达67.5%。在进行对甲砜基甲苯的氧化时,控制电解液浓度为c(Co3+)=0.4 mol/L、c(硫酸)=4.0 mol/L、c(硫酸铵)=0.15 mol/L,n(Co3+)∶n(对甲砜基甲苯)=6∶1,使得反应温度为30℃,反应时间为30 min,对甲砜基苯甲酸的收率可达97.8%,精制后纯度在98.5%以上。     

1-甲基-1-乙氧基-1-糠硫基甲烷合成研究

以乙缩醛 (0 1mol)和糠硫醇 (0 1mol)为原料 ,30～ 35℃下在四氯化碳中反应 2 0min左右 ,合成 1 甲基 1 乙氧基 1 糠硫基甲烷。经红外光谱、色谱、质谱及核磁共振谱检测 ,确证了产物为 1 甲基 1 乙氧基 1 糠硫基甲烷。产率为 6 4 5 % ,产品质量分数为 88 76 %。     

RAFT方法合成的共聚物荧光探针及其氟离子检测性能

本文基于分子间质子转移和诱导分子内电荷转移(ICT)机理,合成了以萘酰亚胺为发光基团、苯甲酰为F-检测基团的荧光单体,并采用可逆加成-断裂链转移(RAFT)聚合方法将其与N-异丙基甲基丙烯酰胺(NIPAM)进行共聚,制备了一种可以用于F-检测的共聚物荧光探针poly(NIPAMm-co-Napn)(简称PNap334),并分别在二氯甲烷-二甲基亚砜(9/1,V/V)溶液和固体薄膜中考察了聚合物PNap334对F-的响应。研究发现,聚合物溶液和聚合物膜对F-均有很好的识别作用,聚合物溶液对F-的检测限为1.05μmol/L。     

配合物Nd_2(C_4H_2O_4)·(C_(10)H_2O_8)_(1.5)·2H_2O的合成及其光电性能的研究

采用水热法合成了顺丁烯二酸和均苯四甲酸二酐与稀土钕的配合物。通过元素分析、红外光谱、紫外光谱、荧光光谱、循环伏安、热重分析等对其进行了表征。室温下的荧光光谱表明,配合物在453.0nm处具有很强的发射峰。电化学性质研究表明,配合物在-0.15~0.15V(vs.SCE)电位范围内具有明显的电化学活性。     

丙烯酸酯卟啉荧光探针的合成及性能

以5-(4-丙烯酸酯基苯基)-10,15,20-三苯基卟啉(APTPP)为荧光增强型探针,对半胱氨酸(Cys)进行特异性检测。以吡咯、苯甲醛、对羟基苯甲醛、丙烯酰氯等为原料合成了产物APTPP,并通过红外光谱、核磁共振谱、元素分析等手段对APTPP结构进行表征,并利用紫外-可见光谱、荧光光谱对其性能进行检测。实验结果表明,APTPP探针对半胱氨酸(Cys)具有特异性选择,半胱氨酸浓度在1.0×10~(-8)~1.0×10~(-7)mol/L范围内,ΔF=4.082+51.60[Cys](10~(-7)mol/L),相关系数R=0.999 3,检出限为2.2×10-9mol/L。     

丙烯酸(2-氯乙基)酯的合成研究

采用强酸性阳离子交换树脂为催化剂,以丙烯酸、氯乙醇为原料合成了丙烯酸(2'-氯乙基)酯,分别研究了反应温度、反应时间、原料配比、催化剂用量和阻聚剂用量等条件对合成反应的影响。得到了合成丙烯酸(2'-氯乙基)酯最适宜的条件是:反应温度为85～95℃,反应时间3h,原料摩尔比n(丙烯酸)∶n(氯乙醇)为0.2∶0.25,丙烯酸为0.2mol的情况下,阻聚剂的用量为0.15g,催化剂的用量1g,丙烯酸(2'-氯乙基)酯的收率可达到91.59%以上。     

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.     

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。     

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.