金刚烷甲酸纤维素酯的合成与表征

以N,N-二甲基乙酰胺/LiCl为溶剂,以对甲苯磺酰氯为共反应剂原位活化金刚烷甲酸,在均相反应体系中合成了新的纤维素高级脂肪酸酯——金刚烷甲酸纤维素酯。采用红外光谱、核磁共振谱进行了表征。热重分析表明,在纤维素链中引入金刚烷基可提高其热稳定性,取代度越高,热稳定性越好。金刚烷甲酸纤维素酯在有机溶剂中的溶解性随取代度增大而提高。     

微波法制备纤维素长链酰基酯及表征

纤维素和高级脂肪酸在均相条件下借助微波辐射合成了纤维素长链脂肪酸酯.当对纤维素/月桂酸/甲苯磺酰氯反应体系进行微波辐照,反应时间从传统加热(80℃)F的24 h下降至90 s,而其产物的取代度最人为2.56,研究了原料配比、微波时间等对产物取代度(DS)、质量收率和摩尔收率的影响以及DS与产物溶解性的关系,并对产物的结构进行了表征.结果表明脂肪酸酯基接枝在了纤维素骨架上,由此制备的纤维素薄膜材料具有一定的机械性能.     

高取代度乙基纤维素合成用稀释剂的实验研究

研究了纤维素乙基化过程中采用不同稀释剂时的效果,探讨了甲苯作为稀释剂时用量的选择及其对醚化剂利用效率的影响。实验结果表明．甲苯是合成高取代度乙基纤维素的良好稀释剂,醚化过程中加入适量甲苯．能够提高产品的乙氧基含量,并且在甲苯与纤维素质量比为8：1时乙氧基含量达到最高;其他反应条件相同时,加入适量甲苯．有利于提高氯乙烷的利用效率。     

月桂酸纤维素酯的均相法合成

在纤维素LiCl/N,N-二甲基乙酰胺(DMAc)均相溶液体系中,以对甲苯磺酰氯(TosCl)为共反应剂,原位活化月桂酸,合成了月桂酸纤维素酯。采用红外光谱、核磁共振、热重等分析手段对产品进行了表征。考察了反应物配比、温度、时间等酯化条件对产品取代度的影响。结果表明:酯化产品的取代度与反应物纤维素葡萄糖苷、月桂酸和对甲苯磺酰氯的配比、反应温度及反应时间有关。在最佳酯化条件下,所得产品的取代度(DS)为2.58。热重分析结果表明,酯化反应削弱了纤维素分子间及分子内的作用力,赋予了月桂酸纤维素酯较好的热加工性。月桂酸纤维素酯在有机溶剂中的溶解度随取代度的增加而提高。     

共反应剂法均相合成长链脂肪酸纤维素酯

在纤维素LiCl/N,N-二甲基乙酰胺(DMAc)均相溶液体系中,以对甲苯磺酰氯(TosCl)为共反应剂,原位活化脂肪酸(RCOOH),合成了长链脂肪酸纤维素酯。采用红外光谱、核磁共振谱、X射线衍射、热重等分析手段对产品进行了表征。考察了脂肪酸含碳原子个数、反应物配比、反应温度、反应时间等酯化条件对产品取代度的影响。结果表明:当反应物纤维素葡萄糖苷(AGU)∶RCOOH∶TosCl=1∶3∶3,反应温度为85℃,反应时间为24h时,产品取代度最高,且随着长链脂肪酸碳原子数目的增加,产物酯化度下降。热重分析结果表明,酯化反应削弱了纤维素分子间及分子内的作用力,赋予了长链脂肪酸纤维素酯较低的热加工温度。长链脂肪酸纤维素酯在有机溶剂中的溶解度随取代度的增加而提高。     

丙烯酸纤维素的合成与表征

以丙烯酰氯为酰化剂与纤维素的(5%-10%)LiCl/DMAc的均相溶液酰化反应,制备丙烯酸纤维素.采用FTIR、元素分析对反应产物进行了结构表征和取代度的测定.探讨反应温度、反应时间、酰化剂用量以及纤维素浓度对反应产物取代度的影响.得到了丙烯酰氯对纤维素较佳酰化反应条件:反应温度为50℃,反应时间为3.5h,丙烯酰氯官能团与纤维素羟基的物质的量之比为3.35,纤维素浓度为1.95%.     

离子液体中羟丙基纤维素的合成

使用离子液体1,3-二乙基咪唑磷酸二乙酯盐([EEIM][DEP])为反应溶剂主组分来溶解微晶纤维素进行羟丙基化衍生,微晶纤维素和醚化剂在离子液体中均可形成均相,通过碱化、醚化、酸化及洗涤等步骤制备得到不同取代度的羟丙基纤维素。考察了碱化反应温度、反应原料摩尔比、醚化反应时间及酸化剂的种类对羟丙基纤维素产品的收率和摩尔取代度的影响,并采用红外、核磁、TGA等手段对产品结构进行了表征。     

S-(-)-对甲苯磺酰乳酸甲酯的合成

研究了以三乙胺为催化剂,二氯甲烷为溶剂,S-(—)-乳酸甲酯和对甲苯磺酰氯发生酰化反应,合成S-(—)-对甲苯磺酰乳酸甲酯的方法,讨论了反应温度、时间、溶剂、催化剂和对甲苯磺酰氯对反应产率的影响。结果表明：n(三乙胺)：n(S(—)-乳酸甲酯)：1：1．2,0～5℃下,对甲苯磺酰氯的二氯甲烷溶液加入S-(—)-乳酸甲酯中,得到S-(—)-对甲苯磺酰乳酸甲酯。通过旋光度、熔点测定及IR分析,证实其结构与预期结构相符。收率为95％,光学纯度95％。     

ATGAP的合成与性能

以1,4-丁二醇为引发剂,三氟化硼乙醚络合物为催化剂,环氧氯丙烷发生开环聚合得到环氧氯丙烷均聚物(PECH).采用磺酸酯法,首先PECH与对甲苯磺酰氯在吡啶介质中反应形成端磺酸酯基氯化聚醚中间体(TsPECH),然后中间体经叠氮化作用形成端基为叠氮基的叠氮缩水甘油醚聚合物(ATGAP).用红外、核磁、碳谱研究化合物的结构.结果表明,所得产物是目标聚合物,ATGAP的玻璃化转变温度为-73 ℃,热分解温度为252.7 ℃,黏度小,可以作为含能增塑剂使用.     

一步法合成乙基纤维素的实验研究

采用正交实验的方法,以甲苯为稀释剂,探讨了乙基纤维素一步法合成的工艺条件。研究结果表明:一步法合成工艺流程简单易行,生产成本较低,产品取代度相对略低,以1mol纤维素为基准,选出优惠工艺条件为:甲苯用量13mol,固体氢氧化钠用量30mol,氯乙烷用量35 mol,反应温度140℃,反应时间12 h,产品乙氧基含量可达44.2%。     

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。