甲基环戊二烯的合成研究

以环戊二烯(CPD)、金属钠和一氯甲烷为原料合成甲基环戊二烯,包括制备环戊二烯钠和环戊二烯钠甲基化两步反应。结果表明,反应温度及环戊二烯与钠的摩尔比对甲基环戊二烯的收率影响显著。双环戊二烯的最佳解聚温度为250℃,对于CPD与钠的反应,反应初期温度应控制在较低的温度,以减少CPD二聚反应;反应后期可将温度升高至28℃,以加快CPD与钠的反应速率。最佳的CPD与钠摩尔比为2.2,此时甲基环戊二烯的收率达86%。     

甲基环戊二烯的合成研究

以环戊二烯（CPD）、金属钠和一氯甲烷为原料合成甲基环戊二烯,包括制备环戊二烯钠和环戊二烯钠甲基化两步反应。结果表明,反应温度及环戊二烯与钠的摩尔比对甲基环戊二烯的收率影响显著。双环戊二烯的最佳解聚温度为250℃,对于CPD与钠的反应,反应初期温度应控制在较低的温度,以减少CPD二聚反应;反应后期可将温度升高至28℃,以加快CPD与钠的反应速率。最佳的CPD与钠摩尔比为2.2,此时甲基环戊二烯的收率达86%。     

三环戊二烯的合成研究

以双环戊二烯(DCPD)为原料,在高温下与解聚生成的环戊二烯(CPD)发生Diels-Alder双烯加成反应,制备非晶型环烯烃(COC)光学材料单体三环戊二烯(TCPD)。考察了反应温度、压力和时间对加成反应的影响,确定较佳的工艺条件为:反应温度150℃,反应压力0.2 MPa,反应时间6 h。在此条件下,TCPD产品收率为82.5%(以原料DCPD计),质量分数为99.5%[面积归一化法(GC)]。产物结构经过~1H NMR和MS表征。     

三步法合成双环戊二烯石油树脂

双环戊二烯(DCPD)主要来自石油裂解制乙烯副产物的C5馏分和煤炭焦化副产物。以DCPD为主要原料,采用三步法进行热聚合反应,得到了高品质的DCPD石油树脂。考察了反应温度、反应时间、原料配比等对DCPD石油树脂的影响,确定了热聚合最佳工艺条件:m(双环戊二烯)∶m(溶剂)∶m(混合碳五)∶m(间戊二烯)=5∶3∶1∶1,第一阶段反应温度200℃,反应时间1 h,第二阶段反应温度260℃,反应时间5 h,第三阶段反应温度200℃,反应时间12 h,成品树脂色度(Gardner)小于4~#,软化点90~110℃,产品收率大于50%。     

二氧化双环戊二烯的合成

以过氧化氢为氧源,磷钨酸及甲基三辛基叔丁胺为催化剂,在水相/有机相两相体系中进行双环戊二烯的环氧化反应,考察了催化剂、溶剂、反应温度和物料配比对反应转化率及收率的影响。结果表明,在反应温度50℃、催化剂磷钨酸用量0.6 g、相转移催化剂甲基三辛基氯化铵用量0.7 g、n(过氧化氢):n(双环戊二烯)=2.0的条件下,20 mL的CHCl_3中反应8 h,双环戊二烯转化率接近100%,收率达94.3%。     

负载型钯催化剂催化环戊二烯选择加氢制环戊烯的工艺研究

工业级的双环戊二烯经解聚-精馏得到高纯度的环戊二烯,以Pd/Al_2O_3为催化剂,对环戊二烯选择加氢制环戊烯工艺进行了研究。实验结果表明,在氢气压力为0.8 MPa、温度为30℃、乙醇与环戊二烯的体积比为2∶1、催化剂加入质量分数为6%的温和反应条件下,环戊二烯的转化率为93.9%,环戊烯的选择性能达到88.6%。但催化剂的循环套用性能有待进一步提高。     

环戊二烯加氢制环戊烯的工艺条件优化研究

以环戊二烯为原料,使用PdCl3为催化剂,甲苯为溶剂,采用间歇式高压反应釜,常温条件加氢制备环戊烯。采用正交实验对环戊二烯加氢过程进行研究,确定了反应温度、催化剂用量、压力、反应时间等因素对加氢过程的影响。优化工艺条件为:反应温度25℃,催化剂比例1.0%(m/m),压力1.5 MPa,反应时间4 h,此时环戊烯的收率达85.5%。     

F/HY催化剂用于挂式四氢双环戊二烯的制备

采用室温过量浸渍法,制备不同F用量改性的HY分子筛催化剂。采用氨程序升温脱附法(NH3-TPD)、X线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)对催化剂的结构及酸性质进行表征,并在桥式四氢双环戊二烯(endo-TCD)制备挂式四氢双环戊二烯(exo-TCD)的反应中考察催化剂的催化性能。结果表明:最适宜的反应条件为以1.0%F/HY为催化剂,活化温度300℃,反应温度240℃,催化剂与原料质量比0.25∶1,溶剂环己烷与endo-TCD的摩尔比10∶1,初始压力1.0 MPa,反应时间1.5 h。最优条件下桥式四氢双环戊二烯的转化率达到92.6%,挂式四氢双环戊二烯的收率达到了59.4%。失活的催化剂可以通过550℃高温焙烧再生,其活性变化不大。     

环戊二烯液相加氢制备环戊烯的研究

介绍了以工业级双环戊二烯为原料,经过解聚-精馏得到高纯度的环戊二烯,以骨架镍为催化剂,对环戊二烯液相加氢制备环戊烯的影响因素进行了研究。结果表明,在反应温度25～30℃,氢气分压为1．0。1．5MPa,无水乙醇作为溶剂,v无水乙醇：V环戊二烯为5～6：1,催化剂用量为4％。5％,搅拌速度为800r／min条件下,反应时间2～3h,环戊二烯的转化率大于98％,环戊烯的选择性大于95％。     

四氢双环戊二烯异构化过程的溶剂效应

采用无水AlCl3为催化剂,考察了使用不同溶剂对桥式四氢双环戊二烯(endo-THDCPD)异构化为挂式四氢双环戊二烯(exo-THDCPD)过程中反应速率、反应转化率、收率、选择性及杂质生成量的影响。采用气相色谱对反应原料、产物及杂质进行定量分析。结果表明溶剂的使用对于异构化反应有显著的影响：甲苯作溶剂时对反应有很大的抑制作用,而1,2-二氯乙烷作溶剂时,则有明显改善,在催化剂浓度3％(wt)、最佳反应温度60℃条件下,反应结果：转化率97．73%、收率97.66％、选择性99．93％。同无溶剂反应时相比,最佳反应温度降低、产物中金刚烷生成量减少同时无焦油产生。实验中以原料endo-THDCPD为对象考察1,2-二氯乙烷作溶剂时的反应动力学,得到了动力学方程。     

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.     

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.     

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。