含POSS聚芴亚胺酮的合成、表征与性能研究

以9,9-双（4-氨基苯基）芴、4,4＇-二溴二苯甲酮及八氨基苯基笼型聚倍半硅氧烷（POSS）为反应单体,通过Buchwald-Hartwig交叉偶联反应,制得了一系列不同POSS含量的POSS基聚芴亚胺酮（PIKF）。通过红外、核磁共振、电子能谱、X射线衍射等对其结构进行了表征,采用热失重分析、紫外/可见光谱及荧光光谱测试了其性能。结果表明,随着POSS含量的提高,聚合物的起始热分解温度逐步升高（从497.62℃升高到508℃和541.61℃）;POSS的引入可有效降低聚集现象的发生,从而使其最大吸收波长红移（从385 nm移至412 nm）;而非共轭大体积POSS基的引入打断了链内共轭,使聚合物的最大发射波长蓝移（从518 nm至490 nm）。     

芴-三苯胺共轭聚合物的合成及性能

采用Heck偶联法制备了2种芴-三苯胺共聚物P1和P2。这2种聚合物均易溶于常用的有机溶剂,如二氯甲烷、三氯甲烷、四氢呋喃等。热性能和光学性能研究结果证实,多面齐聚倍半硅氧烷(POSS)的引入能够提高聚合物的热稳定性,而且能够有效抑制聚集,从而使芴-三苯胺共聚物的紫外吸收和荧光发射光谱蓝移。     

POSS改性环氧树脂的耐热性研究进展

回顾并总结了近年来以笼型倍半硅氧烷(POSS)提高环氧树脂耐热性的研究成果。POSS具有独特的纳米尺寸效应,及其他纳米材料所没有的交联效应,因而能够有效地限制聚合物分子链的活动能力,提高聚合物的玻璃化转变温度和热残余量;此外,POSS的Si-O-Si内核不仅键能高,而且在受热氧作用后能够形成SiO2阻隔保护层,可进一步提高环氧树脂复合材料的耐热性。POSS是一种非常有前途的纳米杂化材料,在降低成本后将能够在环氧树脂耐热性提高方面发挥更大作用。     

9,9-二(丙酸十二氟庚酯)芴共聚物的合成及性能

通过迈克尔加成反应合成单体2,7-二溴-9,9-二(丙酸十二氟庚酯)芴(FDFHP),采用Suzuki偶合反应制备不同FDFHP结构单元含量的含氟聚芴(PF8FDFHP)。通过红外光谱、核磁共振氢谱等方法对其结构和性能进行研究。结果表明:含氟侧链的引入能有效提高聚芴的疏水性,对聚合物的HOMO、LUMO能级没有太大的影响,但使得聚芴在440nm处的荧光发射峰逐渐消失,在500～600nm出现一个新的荧光发射峰。分析认为这是由于含氟侧链的引入使得聚芴的侧链产生结晶,主链之间堆砌更加致密而产生激基缔合物所致。通过不同浓度含氟聚芴溶液的荧光光谱与聚芴的DSC测试对此作了进一步分析。     

POSS基聚合物的热性能和阻燃性

本文介绍了POSS单体和POSS基聚合物的结构、性能和制备方法。重点阐述了各类POSS基聚合物以及它们的热性能。同时简单介绍了POSS对聚合物阻燃性的影响,分析了POSS提高聚合物热性能和阻燃性的原因,并展望了POSS基聚合物的发展方向。     

POSS/聚合物复合材料的制备以及在尼龙中应用的研究进展

多面体低聚倍半硅氧烷(polyhedral oligomeric silsesquioxane,POSS)是一种具有独特中空刚性结构的纳米级材料,作为无机-有机的新型杂化材料,其可设计的分子杂化结构使得POSS能够在聚合物基体中达到分子水平或纳米级别的良好分散,有效提升材料的表面性能、热性能、介电性能和力学性能等,极大地拓宽了在聚合物中的应用领域。本文主要针对POSS的合成制备方法、功能化改性方法、POSS形貌与性能的关系、POSS/尼龙复合材料的制备方法等进行综述。主要介绍POSS的合成方法、官能化方法及POSS/尼龙复合材料的制备方法及结构与性能的关系。未来随着POSS官能化方法的改进必然能够将POSS引入更多的聚合物基体内并实现更好的分散,POSS在聚合物中的应用范围将不断扩大。     

POSS化学改性聚氨酯的研究进展

多面体低聚倍半硅氧烷(POSS)独特的笼型结构可以在分子层面上影响聚氨酯材料体系的软硬链段微相分离程度、链段结晶化和氢键作用。将POSS通过化学方法引入聚不同的氨酯体系中可以提高该类材料的热稳定性、机械性能和耐水性等。从不同的聚氨酯体系出发,介绍了POSS化学改性非水性聚氨酯、水性聚氨酯(WPU)和水性超支化聚氨酯,分析总结了POSS引入到不同体系聚氨酯中对其热稳定性、机械性能和耐水性的影响,以及POSS对其复合材料性能的影响机理。     

国外有关塑料助剂研究的期刊文摘(POSS)

POSS(Polyhedral Oligomeric Silsesquioxane),多面体倍半硅氧烷齐聚物(笼形聚倍半硅氧烷),是近年来研究领域中的热门词汇。由于POSS本身具有的大小规整的纳米尺度和连接的基团的多样性,使得它在塑料等聚合物中被尝试用作添加剂以引入一些特殊的功能或提高复合物的性能。译者希望通过这样一组文献将POSS介绍给工业领域中的读者,共同推进POSS在塑料添加剂领域中的研究和应用。-译者     

POSS改性聚亚苯基硅氧烷的合成与表征

以α,ω-二羟基聚（四甲基对硅亚苯基）硅氧烷为起始原料,分别与1,4-双（甲基氯硅基）苯和甲基二氯硅烷反应,合成了两种带硅氢基的聚亚苯基硅氧烷P1和P2;然后,再与烯丙基七戊基低聚倍半硅氧烷（烯丙基七戊基POSS）进行硅氢加成反应,引入POSS侧基,合成了POSS-P1和POSS-P2。经^1H NMR和^29Si NMR分析证实得到了目标产物;GPC分析表明,两种聚合物经POSS改性后摩尔质量均增大,摩尔质量分布变宽;DSC和TGA分析表明,两种聚合物经POSS改性后熔点分别提高8.4℃和10.6℃,热质量损失率达到5%时的温度分别提高197℃和162℃,且均在400℃以上。     

官能化POSS的制备及其在聚合物改性中的应用进展

介绍了单官能和多官能多面体低聚倍半硅氧烷(POSS)的制备方法:顶端-封角法、三官能团硅烷RSi X3的水解缩合法、官能团衍生法、聚有机倍半硅氧烷的热分解;然后从物理改性和化学改性两方面阐述了POSS改性聚合物的方法;最后总结了官能化POSS在聚合物改性中的应用进展并对其今后的发展方向进行了展望。     

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。