含能粘合剂合成研究新进展(续一)

<正> (上接第4期)4取代环氧丁烷聚合物合成4.1取代环氧丁烷的可控聚合3,3-双(叠氮甲基)环氧丁烷(BAMO)和3-叠氮甲基-3-甲基环氧丁烷(AMMO)均聚和共聚醚以及与四氢呋喃的共聚醚是目前人们研究最为深入的叠氮甲基取代环氧丁烷聚合物。与取代缩水甘油醚单体比较,尽管环氧丁烷和环氧丙烷母体的环张力大致相同,但在阳离子开环聚合过程中,后者存在严重的链“回咬”副反应,生成环齐聚物,使得最终聚合产物的相对分子质量和官能度难以提高。可利用环氧丁烷     

BAMO-AMMO三嵌段共聚物相分离及晶体结构的解析

采用DSC方法研究了3,3’-双叠氮甲基环氧丁烷-3-叠氮甲基-3’-甲基环氧丁烷(BAMO-AMMO)三嵌段共聚物的相分离程度,根据Scherrer公式和Bragg方程计算了pBAMO均聚物和BAMO-AMMO三嵌段共聚物的微晶尺寸和晶面间距,利用XRD比较了两者的结晶度.结果表明,BAMO-AMMO三嵌段共聚物形成...     

PBAMO/GAP三嵌段共聚物的合成和表征

以GAP为起始剂,三氟化硼乙醚为引发剂,通过阳离子开环聚合反应合成出聚3-3-双叠氮甲基氧杂丁烷/叠氮缩水甘油醚(PBAMO/GAP)三嵌段共聚物。用IR、1 HNMR、GPC、DSC和TG方法对产物的结构和性能进行了表征。结果表明,PBAMO/GAP三嵌段共聚物的相对分子质量可控,官能度接近理论值,产物具有热塑性弹性体的性质。产物的分解温度为229℃,具有较好的热稳定性。     

BAMO的能量研究

3,3-双(叠氮甲基)环氧丁烷(BAMO)的分子构架上有两个N_3键。聚BAMO是一种典型的高能叠氮聚合物。因为聚BAMO在室温下为固体,为了制得固体推进剂的高能粘合剂,合成了BAMO和四氢呋喃(THF)的液态共聚物。进行了各种实验,以便阐明BAMO的聚合物、BAMO/THF共聚物以及交链的BAMO/THF共聚物的分解和燃烧过程。它们分解产生的热量是因N_3键断裂生成N_2气造成的。交链的BAMO/THF共聚物的燃速特性主要取决于BAMO和THF的摩尔比。     

丁三醇三硝酸酯与高分子黏合剂的相互作用

运用半经验分子轨道理论PM3方法计算丁三醇三硝酸酯(BTTN)分别与聚乙二醇(PEG)、端羟基聚丁二烯(HTPB)、缩水甘油叠氮基聚醚(GAP)、3-叠氮甲基-3-甲基环氧丁烷聚合物(AMMO)和3,3-双(叠氮甲基)环氧丁烷聚合物(BAMO)等高分子黏合剂所形成的混合体系模型物,求得稳定几何构型.由色散能校正电子相关,求得其结合能.计算结果表明,高分子黏合剂HTPB、AMMO与BTTN的结合能(绝对值)随着高分子聚合度的增加而增大,而BAMO、GAP、PEG与BTTN间的结合能呈不同规律.GAP、AMMO和BAMO与BTTN的结合能略大于HTPB和PEG.     

三乙二醇二硝酸酯与高分子黏结剂在混合体系中的分子间相互作用

用分子轨道(MO)方法在PM3水平上研究三乙二醇二硝酸酯(TEGDN)分别与环氧乙烷/四氢呋喃共聚醚(PET)、聚乙二醇(PEG)、端羟基聚丁二烯(HTPB)、缩水甘油叠氮基聚醚(GAP)、3-叠氮甲基-3-甲基环氧丁烷聚合物(AMMO)和3,3-双(叠氮甲基)环氧丁烷聚合物(BAMO)6种高分子黏结剂所形成的混合体系模型物,求得稳定几何构型。经色散能校正计算,近似求得其相互作用能(ΔE)。整体上讲,AMMO和BAMO与TEGDN的相互作用能大于其他4种高分子黏结剂。其结果为TEGDN与高分子黏结剂之间的相容性研究提供基础数据和理论指导。     

硝化甘油与高分子黏合剂混合体系相互作用的理论研究

运用MO-PM3方法计算了硝化甘油(NG)与高分子黏结剂聚乙二醇(PEG)、端羟基聚丁二烯(HTPB)、缩水甘油叠氮基聚醚(GAP)、3-叠氮甲基-3-甲基环氧丁烷聚合物(AMMO)和3,3-双(叠氮甲基)环氧丁烷聚合物(BAMO)的混合模型体系的几何结构(聚合度n=1,2,3,4),由色散能校正电子相关近似求得其分子间相互作用能(△E).结果表明,当n=4时,5个混合体系的相互作用能为-49～-60kJ/mol.除GAP和BAMO以外,当n值增大时,混合体系的相互作用能增加.混合体系中,两个子体系的原子与原子之间最短距离为0.270～0.340nm.     

3-叠氮甲基-3-乙基氧杂环丁烷及其均聚物的合成与性能

为开发新型含能黏合剂,以三羟甲基丙烷、碳酸二乙酯、对甲苯磺酰氯、叠氮化钠为原料,合成出一种新型叠氮类氧杂环单体3-叠氮甲基-3-乙基氧杂环丁烷（AMEO）。用核磁、红外、元素分析和DSC表征了AMEO的结构与性能。以1,4-丁二醇为起始剂,三氟化硼乙醚络合物为催化剂,二氯甲烷为溶剂,AMMO为单体,借助于阳离子开环聚合,合成出聚3-叠氮甲基-3-乙基氧杂环丁烷（PAMEO）。用红外光谱、核磁共振、元素分析、羟值、数均分子质量表征和测定了聚合物的结构和性能。     

相转移催化法合成BBMO和BAMO

以1,1,1-三溴甲基-1-羟甲基甲烷为原料、水和甲苯为反应溶剂、季铵盐为相转移催化剂,在NaOH的作用下经关环反应合成3,3-双溴甲基氧杂环丁烷(BBMO);以季铵盐为相转移催化剂,BBMO在水相介质中经叠氮基取代反应制备出3,3-双叠氮甲基氧杂环丁烷(BAMO);用红外、核磁表征产品结构,高效液相色谱分析产品纯度.结果表明,BBMO收率与纯度分别为81%和97.2%;BAMO收率与纯度分别为80.9%和98.37%.用相转移催化法制备BBMO和BAMO具有收率高、纯度高、安全性好等特点.     

BAMO-AMMO黏合剂相对分子质量对推进剂力学性能的影响

ETPE(含能热塑性弹性体)具有力学性能好、能量大和不敏感等特性,因而已成为近年来国内外推进剂用黏合剂的理想基体。以BAMO-AMMO(3,3-二叠氮甲基氧杂环丁烷/3-甲基-3-叠氮甲基氧杂环丁烷嵌段共聚物)作为ETPE,制备了固体推进剂用黏合剂,并着重探讨了BAMO-AMMO黏合剂的Mr(相对分子质量)对推进剂力学性能、动态力学性能和微观结构等影响。研究结果表明:随着黏合剂Mr的增加,推进剂的高温拉伸强度、低温断裂伸长率、储能模量和弹性等均随之增大,而Tg(玻璃化转变温度)降低;然而,当黏合剂Mr过高时,推进剂复合体系中易出现分层现象。     

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.     

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.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.