苯乙酮-环己酮-甲醛共缩聚树脂的合成研究

以苯乙酮、环己酮和甲醛为原料,氢氧化钠为催化剂合成苯乙酮-环己酮-甲醛共缩聚树脂,研究了环己酮/苯乙酮摩尔比、预反应时间、甲醛加料方式等对树脂软化点和羟值的影响,借助FT—IR及^1H-NMR对聚合产物进行了表征。发现在醛酮摩尔比为1．3、环己酮/苯乙酮摩尔比为1．0、氢氧化钠用量为3．0％（质量分数）、预反应时间为1．5h、甲醛一次性加入时,可获得软化点为51．3℃、羟值为119．0mgKOH／g的苯乙酮-环己酮-甲醛树脂。FT—IR和^1H—NMR结果表明通过预反应有利于苯乙酮参与共缩聚反应。     

苯乙酮1，2-丙二醇缩酮的合成研究

以强酸性阳离子交换树脂为催化剂,通过苯乙酮和1,2-丙二醇反应合成苯乙酮1,2-丙二醇缩酮,系统的研究了酮醇物质的量之比、催化剂用量和反应时间等因素对产品收率的影响。结果表明：在酮醇物质的量比为1：2,催化剂用量为反应物总质量的0．6％,环己烷为带水剂,反应时间3h的优化条件下,产率达79．8％。     

钠催化热固性酚醛树脂的合成与表征

采用苯酚和37%甲醛水溶液为原料并以30%氢氧化钠溶液为催化剂制备了高羟甲基含量、低残留甲醛和工艺稳定的热固性酚醛树脂。通过测试合成的树脂中游离酚、游离醛和羟甲基含量研究了醛、酚物质的量比(F/P)、催化剂用量、反应时间和反应温度对酚醛树脂合成的影响,并通过傅里叶变换红外光谱对合成树脂的结构进行了分析。结果表明:当F/P=1.5,催化剂添加质量分数为5%,反应时间2.5 h,反应温度85℃时,制备的树脂性能最佳,其羟甲基含量最高,树脂活性最大,主要为高邻位结构。     

2,2-二羟甲基十二酸的合成

研究了以月桂醛(正十二醛)、甲醛、过氧化氢为原料,经羟醛缩合、过氧化氢氧化合成2,2-二羟甲基十二酸的方法,探讨了原料摩尔比、催化剂或氧化剂用量、反应温度和时间对羟醛缩合反应和氧化反应的影响。结果表明,月桂醛(正十二醛)与甲醛摩尔比为2.6∶1.0、催化剂与月桂醛摩尔比为0.51∶1.0、羟醛缩合反应温度为50℃、反应时间为3 h,合成的2,2二-羟甲基十二醛收率为46%;H2O2与2,2二-羟甲基十二醛摩尔比为1.1∶1.0,氧化反应温度为70℃、反应时间为7 h,合成的2,2二-羟甲基十二酸收率为86%。并用13C和1H核磁共振谱表征了2,2-二羟甲基十二酸的结构。     

水溶性环己酮-三聚氰胺-甲醛共缩聚树脂的合成与表征

以环己酮、三聚氰胺、甲醛为原料,氢氧化钠为催化剂,用"两步法"合成出环己酮-三聚氰胺-甲醛树脂(CMFR),考察了三聚氰胺用量、醛酮物质的量比、催化剂用量及反应时间等对CMFR的游离甲醛含量及溶水倍数的影响,并借助FT-IR、13C-NMR、DSC、TG等对CMFR进行了表征。发现在环己酮、三聚氰胺、甲醛物质的量比为1.0∶0.2∶2.0,催化剂用量为0.6%,反应时间为120min,反应温度为90℃的条件下,合成出的CMFR游离甲醛含量为0.45%,溶水倍数为8.2。FT-IR和13C-NMR结果表明CMFR分子中存在三聚氰胺结构;DSC分析表明CMFR仅存在一个固化放热峰,说明三聚氰胺参与了树脂的共缩聚反应,形成了均一的分子结构,其固化温度约为182.5℃,固化后CMFR的耐溶剂性能提高。     

低游离醛高羟甲基含量酚醛树脂的合成

通过实验,以CaO作催化剂合成了低游离醛高羟甲基含量酚醛树脂。采用正交试验方法研究了催化剂用量、反应温度、反应时间对酚醛树脂的游离醛含量、羟甲基含量2个指标的影响。当n(苯酚)∶n(甲醛)=1∶1 2～1 3时,最优工艺条件为:n(催化剂)∶n(苯酚)物质的量比0 02、反应温度70℃、反应时间3h。     

高羟甲基含量甲阶酚醛树脂的合成

利用KOH作催化剂,以甲醛和苯酚为原料合成了一种高痉甲基含量的甲阶酚醛树脂,通过羟甲基含量、可被溴化物含量、固有粘度的测定和甲醛转化率的计算,研究了反应条件对合成的影响。结果表明：随着反应温度的升高、甲醛和KOH用量的增加、反应时间的延长,树脂中的羟甲基含量先增加,后减小,树脂的固有粘度则逐渐增大,其中反应温度和催化剂用量的变化树树脂固有粘度的影响较大。在65℃的条件下,n（甲醛）：n (醛酚）：n（氢氧化钾）为2．5：1：0．1时,反应,甲阶酚醛树脂中的羟甲基质量分数可以达到32．8％,固有粘度达到2．68ml.g^-1。并用红外光谱对树脂的结构进行了表征。     

苄基三氮唑查尔酮的合成

以丙炔醇为原料,两步反应得到1-苄基-1,2,3-三氮唑查尔酮,再与邻羟基苯乙酮发生羟醛缩合反应,高效的得到新型苄基三氮唑查尔酮,并通过1H NMR,13C NMR,HRMS对目标产物进行了表征。通过考察反应溶剂、反应时间以及醛酮投料比对产物收率的影响,确定了最优反应条件:以甲醇为反应溶剂,回流反应3 h,醛酮投料比为1∶1.2时,目标产物反应产率相对较高,目标产物产率为88%。     

(1E,4E)-1-(4-溴苯基)-5-苯基-1,4-戊二烯-3-酮的合成方法研究

以苄叉丙酮和醛为原料,氢氧化钠水溶液为催化剂,采用两条路线合成了(1E,4E)-1-(4-溴苯基)-5-苯基-1,4-戊二烯-3-酮。考察了物料比、催化剂及其用量、反应温度、溶剂等因素对反应产率的影响。实验结果表明:苄叉丙酮与醛的物料比为1∶1.05,5%NaOH水溶液30 mL为催化剂,15 mL乙醇为溶剂,室温下进行反应。产率分别为84.6%和89.3%。通过熔点、IR和1H NMR确定了产物的结构。     

常温呈固体的热固性酚醛树脂的合成及表征

以苯酚、37%甲醛水溶液为原料,25%氨水为催化剂,合成了常温呈固态的热固性酚醛树脂。通过软化点,凝胶化时间,羟甲基含量及酚醛树脂固化度测试研究了醛酚比(F/P)、反应温度及反应时间对合成树脂的结构及性能的影响。结果表明:F/P=2.0,反应温度65℃、反应时间4.0 h时合成的树脂固化速度最快,羟甲基含量最高。     

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。