雷尼镍催化加氢合成7-氟-2H-1,4苯并噁嗪-3(4H)-酮

研究了雷尼镍为催化剂加氢还原2-(5-氟-2-硝基苯氧基)乙酸甲酯(1)合成7-氟-2H-[1,4]苯并噁嗪-3(4H)-酮(2)的方法,使还原、合环一次完成。考察了反应温度、催化剂、氢气压力、时间、溶剂及回收的催化剂和溶剂对反应收率的影响,确定了合成工艺条件:反应温度70℃,反应时间4h,催化剂用量为原料质量的5%,氢气压力5MPa,溶剂甲醇用量为1000mL/mol1。产品的收率92.4%,含量98%,溶剂和催化剂循环使用4次,对收率无影响。产品结构经元素分析、红外光谱、核磁共振确证。     

锰卟啉仿生催化制备1,2-环氧丁烷

制备了四苯基卟啉、四(4-甲基苯基)卟啉、四(4-甲氧基苯基)卟啉、四(4-氟苯基)卟啉、四(4-氯苯基)卟啉及其对应的锰卟啉,并对其结构进行了表征。以前述卟啉为催化剂,催化1-丁烯环氧化制备1,2-环氧丁烷。考察了催化剂种类、催化剂浓度、丁烯用量、共还原剂用量、溶剂用量、转速、反应时间、反应温度、反应压力对反应结果的影响。结果表明,以四(4-氟苯基)锰卟啉为催化剂,在催化剂浓度为8×10~(-6)mol/L、丁烯用量为1. 9 L、丙烯醛用量为3 mL、溶剂用量为200 mL、转速为500 r/min、反应压力为1. 6 MPa、反应温度为103℃、反应时间为60 min的条件下,1-丁烯转化率为96. 39%,1,2-环氧丁烷收率为95. 04%,选择性为98. 61%。     

Pt/C催化加氢3-氯-4-甲基硝基苯制备3-氯-4-甲基苯胺

3-氯-4-甲基苯胺是合成有机颜料、染料和农药的重要有机中间体。以3-氯-4-甲基硝基苯为原料,1%Pt/C为催化剂,低压催化加氢制备3-氯-4-甲基苯胺,考察不同溶剂、反应压力、反应温度和催化剂用量对产物收率的影响。结果表明,在3-氯-4-甲基硝基苯10 g、溶剂甲醇用量30 m L、1%Pt/C催化剂用量0.04 g、反应温度80℃和反应压力1.0 MPa条件下,3-氯-4-甲基苯胺收率99.08%,脱氯率0.2%,催化剂可重复使用5次。     

Raney-Ni催化加氢合成2,3,5-三甲基氢醌的研究

以Raney-Ni为催化剂在乙酸丁酯溶剂中,间歇催化2,3,5-三甲基苯醌(TMBQ)加氢合成2,3,5-三甲基氢醌(TMHQ)。通过正交实验考察了催化剂用量、溶剂用量、温度及压力等对反应的影响。结果表明,较优反应条件为:TMBQ初始浓度为0.1 g/mL,催化剂量为TMBQ的10%,氢气压力0.7～0.8 MPa,温度为100℃(转速800 r/min)。TMHQ加氢收率可达97.3%。溶剂通过水蒸气蒸馏回收,总收率93.1%。     

改性Raney Ni催化剂用于加氢合成间苯二甲胺

采用改性RaneyNi催化剂 ,研究了溶剂、温度、压力、催化剂用量对间苯二甲腈 (IPN)加氢合成间苯二甲胺 (m XDA)反应的影响。结果表明 ,该催化剂在以甲醇、甲苯为混合溶剂 ,V(甲醇 )∶V(甲苯 )=1∶2 ,当m(溶剂 )∶m(IPN) =3∶1,反应温度 70℃、压力 6 0～ 7 0MPa、催化剂用量为原料质量 10 %时 ,IPN转化率接近 10 0 % ,m XDA收率达 97%。失活催化剂经再生 ,即能恢复其性能。     

无碱条件下氧气催化氧化2-乙基己醇合成2-乙基己酸

以2-乙基己醇作为原料,O_2作为氧化剂,无碱参与下催化氧化合成2-乙基己酸。使用气相色谱(GC)进行定量分析,气质联用仪(GC-MS)进行定性分析。考察了催化剂、溶剂、反应温度、时间及氧压力对反应的影响。结果表明:2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)/硝酸铜为合适的催化剂体系,乙酸乙酯为合适的溶剂。适宜的反应条件是:催化剂TEMPO用量为2-乙基己醇物质的量的5%、硝酸铜用量为2-乙基己醇物质的量的4%,100℃、0.5 MPa O_2压力下反应6 h,2-乙基己酸收率可达77.1%。O_2恒压条件下该反应是拟一级反应,反应活化能为59.9 k J/mol。主要副产物是3-庚醇和3-庚酮。     

锡卟啉的合成及其绿色催化氧化环己烯

考察催化剂金属锡次卟啉二甲酯催化氧化环己烯的反应性能。探讨了在催化氧化过程中,反应温度、压力、时间、催化剂用量等因素对环己烯转化率和产物选择性的影响,并结合GC-MS在线分析检测。结果表明,当温度100℃、压力0.8 MPa、时间7 h、催化剂用量0.5 mg(7.6×10-4mmol)、环己烯10 mL(98 mmol)的条件下,环己烯的转化率达84%,相应产物2-环己烯-1-醇和2-环己烯-1-酮的总选择性为94%,并对该反应的催化氧化反应机理进行了初步研究。     

锡卟啉的合成及其绿色催化氧气氧化环己烯

考察催化剂金属锡次卟啉二甲酯催化氧化环己烯的反应性能。探讨了在催化氧化过程中,反应温度、压力、时间、催化剂用量等因素对环己烯转化率和产物选择性的影响,并结合GC-MS在线分析检测。结果表明,当温度100℃、压力0.8 MPa、时间7 h、催化剂用量0.5 mg(7.6×10-4mmol)、环己烯10 mL(98 mmol)的条件下,环己烯的转化率达84%,相应产物2-环己烯-1-醇和2-环己烯-1-酮的总选择性为94%,并对该反应的催化氧化反应机理进行了初步研究。     

甲苯液相氧化法制取苯甲醛的改进研究

文章研究了用气-液-固非均相反应器进行的甲苯液相空气氧化法制取苯甲醛,采用自制的主催化剂ME05(氧化铜和丁酸锰的混合物)和助催化剂ME12(摩尔比为1的氯化铵和氯化钾)、溶剂丁酸、引发剂苯甲醛。获得的最佳反应工艺条件是主催化剂ME05、助催化剂ME12、溶剂丁酸、引发剂苯甲醛的用量分别占甲苯质量的0.1%、0.002%、10%和0.001%,反应温度110℃,反应压力0.8MPa,反应时间2h,此时苯甲醛的单程收率可达到21.1%。     

过氧磷钼钨酸盐催化一步法合成2-羟基-1,4-桉树脑

以过氧磷钼钨酸烷基吡啶盐Cat-PMo2W2O24为氧化-酸双功能催化剂,在质量分数为30%的双氧水存在下,催化松油烯-4-醇(Ⅰ)一步合成了2-羟基-1,4-桉树脑(Ⅱ)。溶剂种类、催化剂用量、双氧水用量能明显改变催化反应体系的相态、酸性或酸量,进而影响反应转化率和产率。最佳的反应条件为:松油烯-4-醇12 mmol,溶剂氯仿5 m L,催化剂用量为4.20%(以松油烯-4-醇的质量计),双氧水用量为0.91(以双氧水与松油烯-4-醇的摩尔比计),反应温度为25℃,反应时间为30 min;在该条件下,松油烯-4-醇的转化率和2-羟基-1,4-桉树脑的产率分别为96.2%和70.1%。     

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.