脂肪酸烷醇酰胺磷酸酯表面活性剂的合成及性能研究

以C14~18的脂肪酸与二乙醇胺反应合成了系列脂肪酸烷醇酰胺,再经磷酸化反应及中和反应制备了6种脂肪酸烷醇酰胺磷酸酯盐表面活性剂。分别测定了各产物的组成及表面活性,考察了无机盐对表面张力(γ)及临界胶束浓度(cmc)的影响,测试了不同碱中和产物水溶液与系列烷烃间的界面张力。结果表明,脂肪酸碳数为14,16和18的烷醇酰胺磷酸酯盐表面活性剂的cmc分别为50,50和30 mg/L,γcmc为26~31 mN.m-1;无机盐对产物的cmc影响不大;在质量分数为0.3%时,6种表面活性剂水溶液与正构烷烃形成最低界面张力的最小烷烃碳数为10~16,其中用NaOH中和得到的C14N与十二烷、十四烷以及C16N与十六烷均可达到超低界面张力,分别为0.007 8,0.008 3和0.001 6 mN.m-1,用二乙醇胺中和得到的C14D也可与癸烷达到超低界面张力。     

头基含羟基的季铵盐双子表面活性剂的合成与性能

以溴代烷、二乙醇胺和1,4-二溴丁烷为原料,通过两步反应合成了一类头基含羟基的季铵盐双子表面活性剂亚丁基-1,4-双(烷基二羟乙基溴化铵)(m-4-m(OH),m=8,10,12,14),通过核磁共振氢谱(~1H NMR)和质谱(MS)对中间体和目标产物的结构进行表征。通过表面张力仪和电导率仪测定m-4-m(OH)在水溶液中的平衡表面张力(γ_(cmc))和临界胶束浓度(cmc),并测定了其水溶液的乳化性能和泡沫性能。结果表明,烷基链越长,表面活性剂越容易自发形成胶束,14-4-14(OH)的cmc最低,可达0.48 mmol/L,γ_(cmc)为33.6 mN/m;头基中引入羟基可有效降低表面活性剂的cmc和γ_(cmc);随着烷基链的增长,乳化性能越好;起泡性随着烷基链的增长呈先升后降的趋势。     

N-十二烷基亚氨基二乙酸钠水溶液性质的研究

合成了N-十二烷基亚氨基二乙酸钠(C12H25N(CH2COONa)2)。研究结果表明,分子中的亚氨基在水溶液中极易水解结合质子,使溶液pH随C12H25N(CH2COONa)2浓度增大而增大,羧基则基本处于碱式形态。这种两性分子形式使其水溶液的表面张力曲线具有明确的转折点,而不象月桂酸钠那样出现最低点。该转折点表示临界胶团浓度cmc(=22.1 mmol.L-1)。最低表面张力γcmc和降低水表面张力20 mN.m-1所需的表面活性剂浓度c20分别为44.8 mN.m-1和10.5 mmol.L-1。     

三烷基苯磺酸盐的合成与表面性能研究

为了研究三直链烷基苯磺酸钠的分子结构与表面活性之间的关系,以3,4-二甲基-4-氯苯为原料,经格林试剂交叉耦合反应、氢碘酸改进法还原反应、磺化反应以及中和反应等步骤,合成了2种不同烷基长碳链的三直链烷基苯磺酸钠(分别记为a和b),产物的总收率达45%～53%。用两相滴定法测定产物的纯度均大于99%,并用红外光谱进行了结构鉴定。25℃时用滴体积法测定表面活性剂a和b水溶液的表面张力和临界胶束浓度(cmc),分别为31.15 mN/m,25.48 mN/m和3.28×10-4mol/L,8.13×10-4mol/L。结果表明,随着长碳链碳原子数的增加,表面活性剂的cmc逐渐减小,临界胶束浓度下的表面张力(γcmc)逐渐增大。     

全氟辛酸钠复配体系对1-萘甲氧基乙酸溶液表面张力的影响

为了提高植物生长调节物质1-萘甲氧基乙酸溶液的润湿性和渗透性,将其与碳氢碳氟表面活性剂进行复配。采用表面张力法测定复配体系的表面张力。结果表明,1-萘甲氧基乙酸复配体系的胶团生成能力、降低水表面张力的能力和效率均出现明显的增效。综合考虑cmcT(临界胶束总浓度)、γcmc、c20,T(表面张力比纯水降低20 mN.m-1时表面活性剂总浓度)及经济效益,全氟辛酸钠(SPFO)/十二烷基三甲基溴化铵(DTAB)/KCl复配体系的效果最佳(SPFO与DTAB摩尔比为1∶10,KCl为0.1 mol.dm-3)。这3个指标分别为3.1×10-4mol.dm-3、18.8 mN.m-1、9.2×10-6mol.dm-3。     

可断键均三嗪脂肪磺酸盐型表面活性剂的合成与表面活性

以脂肪胺、三聚氯氰、氨基乙磺酸为原料合成了4种不同碳链长度均三嗪脂肪磺酸盐型表面活性剂[2-脂肪胺基-4-(2-磺基乙基)胺基-6-氯-1,3,5-均三嗪]。用元素分析、1HNMR、FTIR对中间体和目标产物的结构进行了表征。测定了25℃时4种表面活性剂的表面张力,研究了它们的表面活性。结果表明,疏水链长为C14时,该类表面活性剂的临界胶束浓度(cmc)和cmc下的表面张力(γcmc)达到最低值分别为:3.58×10-5mol/L和32.53 mN/m。与普通表面活性剂C12-LAS相比,疏水链长为C12~C16的该类表面活性剂的cmc均比C12-LAS低1~2个数量级,即它们降低水溶液表面张力的效率比C12-LAS高;疏水链长为C8、C12和C16时,其在溶液表面的饱和吸附量均比C12-LAS小,饱和吸附面积比C12-LAS大;疏水链长为C14时则相反。     

非对称双子季铵盐阳离子表面活性剂的合成及性能

以十二烷基二甲基叔胺、盐酸、环氧氯丙烷为原料,合成了中间体N-(3-氯-2-羟丙基)-N,N-二甲基十二烷基氯化铵,后与3种不同烷基链长的长链烷基叔胺反应,得到3种非对称Gemini季铵盐阳离子表面活性剂(Ⅰ～Ⅲ)。通过IR光谱,1HNMR确证了中间体及目的产物的结构。测定了产物的临界胶束浓度cmc及γcmc。cmc分别为1 07×10-3mol·dm-3、1 99×10-3mol·dm-3和9 55×10-3mol·dm-3,γcmc分别为40 9mN·m-1、48 0mN·m-1和50 9mN·m-1。结果表明:所合成的非对称Gemini季铵盐阳离子表面活性剂具有较高的表面活性。     

一种三硅氧烷硫酸盐表面活性剂的合成及性能

以1,1,1,3,5,5,5 -七甲基三硅氧烷(TSO)、甲基丙烯酸羟丙酯和氨基磺酸为原料合成了一种三硅氧烷硫酸盐表面活性剂;通过IR和1HNMR对合成的中间体及最终产物的结构进行了表征,并对其表面活性、泡沫性能和渗透性能等进行了测试.结果表明,三硅氧烷硫酸盐表面活性剂的最低表面张力(γcmc)为23.3 mN· m-1,临界胶束浓度(cmc)为3.16×10-2 tmol·L-1;该表面活性剂有较好的渗透性能,但是起泡性和稳泡性不强.     

一种阴离子型双子表面活性剂的合成与表征

以乙二胺、2-溴乙基磺酸钠、月桂酸等为主要原料制备了阴离子型双子(gemini)表面活性剂N,N′-乙撑双[(N-乙磺酸钠)-十二酰胺](DTM-12),以IR和1HNMR对其结构进行了表征。该目标产物水溶液的cmc(5.0×10-4mol/L)是十二烷基磺酸钠和十二烷基硫酸钠的1/20和1/16,γcmc(29.7 mN/m)比它们低8 mN/m~10 mN/m。DTM-12分别与DTAB和Triton X-100组成的复配体系在摩尔比为3∶7时,cmc达到1.06×10-4mol/L和0.49×10-4mol/L,γcmc达到25.4 mN/m和31.7 mN/m,DTM-12表现出较好的协同效应。DTM-12还具有良好的润湿力。     

脂肪醇聚氧乙烯醚（EO6）磺酸盐的合成及性能研究

以C14～18的脂肪醇与环氧乙烷反应合成了系列脂肪醇聚氧乙烯醚,再以氢化钠为催化剂、丙烷磺内酯为磺化剂合成了脂肪醇聚氧乙烯醚(EO6)磺酸钠(14AES6,16AES6和18AES6)。通过测定反应时间与磺化率的关系,得到14AES6,16AES6和18AES6较佳的磺化时间;测定了产物在蒸馏水、油田采出水和CaCl2水溶液中的表面活性(cmc及其对应的γcmc);评价了产物与不同碳数烷烃及胜利临盘油田原油的界面张力,确定了原油的等效烷烃碳数。实验结果表明,14AES6,16AES6和18AES6的较佳磺化时间分别为8,12和16 h;3种产物在蒸馏水中的cmc为0.02%,0.01%和0.005%,γcmc分别为30.52,37.55和35.59 mN·m-1;在临盘油田矿化水中的cmc减小了0～0.01%,γcmc降低了0.81～1.38 mN·m-1;在3种不同浓度CaCl2溶液中16AES6的cmc均为0.005%,低于在蒸馏水中的情况,γcmc略有降低;16AES6和18AES6的最小烷烃碳数分别为10和12,通过测试含有助剂的18AES6体系与原油及烷烃间的界面活性得临盘油田原油的等效烷烃碳数为13。     

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。