含二氮杂萘酮联苯结构耐高温聚氨酯胶的合成

采用本体聚合,将自制的含有4—(4’—羟基苯基)—2,3—二氮杂萘—1—酮(DHPZ）^[1—3]作为单体引入双组分聚氨酯的固化剂中,合成了一类新型的含杂萘三联苯结构的聚氨酯胶粘剂。DHPZ的扭曲和非共平面杂环结构使聚合物难以实现长程有序。从而提高了其刚性和耐高温性能。常温拉伸强度不低于20MPa,而且具有较强的耐酸,耐水水解性能。以FT-IR,DSC,TGA等分析手段研究了聚合物的结构和耐热性能。结果表明,新型聚氨酯胶粘剂具有高的玻璃化转变温度（Tg=340～370K）,氮气氛中10%热质量损失温度为570K,在520K的温度下无热质量损失。该胶粘剂可以在高温条件下使用。     

新型含二氮杂萘酮结构——聚氨酯清漆的合成及性能

针对传统通用型聚氨酯涂层材料耐高温性欠佳的缺点，本文通过分子结构设计，将全芳环非公平面、扭曲的二氮杂耐酮联苯结构引入聚氨酯主链中，首次合成了含二氮杂萘酮联苯结构聚氨酯树脂，研究其结构性能关系，并将其应用于涂料领域。以TDI、TMP和自制的4-(4’-羟基苯基）-2，3-二氮杂萘-1-酮(DHPZ)为原料，以简便的工艺制备了结构新颖的含二氮杂萘酮结构的单组份聚氨酯清漆PUv-C。以傅立叶红外变换手段(FT-IR)表征了聚氨酯涂层树脂的结构。以差示扫描量热仪(DSC)和热重分析仪(TGA)等分析手段研究了聚氨酯涂层树脂的耐热性能。     

含二氮杂萘联苯结构聚氨酯的合成与性能研究

以聚己内酯二醇(PCL)、4-(4'-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)、4,4'-二苯基甲烷二异氰酸酯(MDI)及1,4-丁二醇为原料,采用一步法设计合成了含二氮杂萘联苯结构聚氨酯溶液。采用红外光谱仪、X射线衍射仪、热重分析仪以及万能力学试验机,考察了DHPZ含量对聚氨酯胶膜耐高温性能和力学性能的影响。结果表明,二氮杂萘联苯结构提升了聚氨酯膜的耐热性能,DHPZ质量分数从0到5%,初始热分解温度(T_d~(1%))可提高10～20℃;当DHPZ质量分数为2%时,聚氨酯膜力学性能较优,其拉伸强度达到67. 1 MPa,断裂伸长率为860%,弹性模量为4. 5 MPa。     

MM-HPPZ/NDA/TPA聚芳酰胺的合成与性能

采用新型的含间甲基取代杂萘联苯结构的二胺2-(4-氨基苯基)-4-[2-甲基-4-(4-氨基苯氧基)卜2,3-二氮杂萘-1-酮为单体,与2,6-萘二甲酸(NDA)进行溶液缩聚制备了新型聚芳酰胺,以对苯二甲酸(17PA)为第三单体对聚芳酰胺进行了共缩聚改性,并研究了TPA的含量及结构对聚芳酰胺性能的影响。n(NDA)/n（TPA)为4：6时,共聚物特性黏数最大为1．70dL/g。合成的聚芳酰胺具有良好的溶解性,可溶于N-甲基吡咯烷酮、N,N-二甲基乙酰胺等非质子极性溶剂中,玻璃化转变温度大于320℃,5％热失重温度大于435℃。     

含氟杂萘联苯型聚醚酰亚胺共聚物的合成

2，2′-双(3，4—二羧酸)六氟丙烷二酐和2—(4—氨基苯基)—4—[4—(4—氨基苯氧基)苯基]—2，3—二氮杂萘—1—酮分别与4，4′-二氨基二苯醚、4，4′—二氨基二苯砜在间甲酚中进行“一步法”溶液共聚合，制备了2种共聚聚醚酰亚胺。通过差示扫描量热法、热失重，傅里叶变换红外光谱、核磁共振氢谱对聚合物进行了表征。聚合物具有优异的耐热性能，玻璃化转变温度高于300℃，热失重温度高于500℃。同时，聚合物在常用非质子有机极性溶剂中具有优良的溶解性能。     

高耐热聚芳醚酮固化邻苯二甲腈树脂

以4-(4-羟基苯基)-2,3-二氮杂萘-1-酮、4,4’-二氟二苯甲酮和4-氨基苯酚为原料，通过两步一锅法合成了一种新型的氨基封端杂萘联苯聚芳醚酮(A-PPEK)，采用差示扫描量热法(DSC)探究了其对间苯二酚基邻苯二甲腈(DPPH)的固化性能。相比于常用的芳香二胺固化剂4,4’-二氨基二苯砜(DDS),A-PPEK的5%热失重温度(T_d5%)提高了69.3℃。另外，与DDS在400℃时快速升华不同，A-PPEK在相同温度下的质量保留率仍>95%，说明A-PPEK可以有效解决小分子固化剂高温下分解，容易在邻苯二甲腈树脂中形成缺陷的问题。一系列实验表明，以A-PPEK固化DPPH，体系具有优异的耐热性和加工流动性，当A-PPEK含量为DPPH质量的10%时，固化树脂的T_d5%可达553.2℃，玻璃化转变温度高于实验测试范围380℃，最低黏度可达0.167 Pa·s。     

新型耐热双马来酰亚胺改性环氧树脂性能研究

以4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)为原料,制得含二氮杂萘酮结构的聚芳醚砜预聚物(PPES),再与顺丁烯二酸酐反应得到不同聚合度的含二氮杂萘联苯结构的双马来酰亚胺(PPES-BMI)。采用FT-IR和1H-NMR对其分子链结构进行了表征,测试了聚合物分子质量和溶解性能。通过TGA分析和冲击性能测试研究了不同含量、不同聚合度的PPES-BMI对PPES-BMI/DGEBA复合体系热-力学性能的影响。结果表明,PPES-BMI含量增加,体系初始热分解温度和最大热失重温度上升;PPES-BMI质量分数为35%,DP=20的PPES-BMI/DGEBA共混体系的冲击强度最大,达到2.67 kJ/m2,增幅为75.8%。     

耐高温新型含杂萘联苯聚醚砜嵌段共聚物的性能

将氯端基聚醚醚砜齐聚物和杂萘联苯类双酚羟端基齐聚物通过溶液缩聚,成功地合成了一系列新型聚醚醚砜-聚醚砜(PEES-PPES)嵌段共聚物,并用IR、DSC、TGA、X-WAXD等测试手段对聚合物进行了表征。结果表明:PEES-PPES具有较高的热稳定性,较好的溶剂溶解性;砜基比例的变化对PEES-PPES的热性能有较大的影响,表明砜基对杂萘联苯聚醚砜改性效果明显。     

新型间甲基取代杂萘联苯型聚芳酰胺的研制

采用间甲基取代杂萘联苯型类双酚4-(2-甲基-4-羟基苯基)-2,3-二氮杂萘-1-酮与对氯苯腈反应制得二腈化合物,进一步水解为二酸,以此新型二酸与三种二胺聚合制得的三种新型聚芳酰胺均具有较高的耐热性能,其玻璃化转变温度在287～317℃,且易溶于非质子极性溶剂中,聚合物的特性粘数为1.62～1.83 dL/g,拉伸强度为87～98 MPa,断裂伸长率为6.4％～8.4％,拉伸模量为0.7～1.3 GPa,表面电阻系数为10~(14)Ω,体积电阻系数达10~(17)Ω·cm。     

含二氮杂萘酮联苯结构双马来酰亚胺的合成

由含二氮杂萘联苯酮结构的芳香族二元胺4-[4-(4-氨基苯氧基)苯基]-2-(4-氨基苯基)二氮杂萘-1-酮(DHPZ-DA)与顺丁烯二酸酐(MA)反应得到了含二氮杂萘酮联苯结构的双马来酰亚胺预聚物(DHPZ-BMI),并对其进行了FT-IR红外及1H-1H COSY NMR核磁表征。对其溶解性的研究表明,DHPZ-BMI易溶或部分溶解于一些常见低沸点极性溶剂,如氯仿、丙酮。利用示差扫描量热仪(DSC)对DHPZ-BMI热行为进行了研究,结果表明该预聚物的熔点较高,熔融和固化过程的温度范围在低升温速率下有所重叠。为此,加入不同含量的2,2′-二烯丙基双酚A(DABPA)改善其工艺性,并采用DSC对其热性能进行了初步研究,结果表明DABPA的加入,可明显改善树脂的固化行为。     

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。