间苯二甲酸酯Gemini表面活性剂的合成及性能

N,N-二甲基乙醇胺与间苯二甲酰氯反应获得二(N,N-二甲基胺基乙基)间苯二甲酸酯,再分别与溴代正十二烷和溴代正十六烷制得两种含酯基Gemini阳离子表面活性剂(C12-O-C12、C16-O-C16)。采用IR、1 H NMR、元素分析表征了其结构。测定了其临界胶束浓度(CMC)分别为6.91×10-4 mol/L、7.07×10-5 mol/L;平衡表面张力(γCMC)分别为41.9 mN/m、40.8 mN/m;Krafft点分别为0℃、43℃。并研究了其乳化性、泡沫性质等。     

Gemini表面活性剂C12-3-C12·2Br及C12-3(OH)-C12·2Cl的合成及表面活性

合成了联结基团分别为亚甲基链及含羟基亚甲基链的两种季铵盐Gemini表面活性剂,即C12-3-C12.2Br及C12-3(OH)-C12.2Cl。用红外光谱、核磁共振及元素分析对它们的结构进行了鉴定,并对影响反应的因素进行了研究,得出了合成C12-3-C12.2Br的最佳条件为:n(N,N-二甲基十二烷基胺)∶n(1,3-二溴丙烷)=2.2∶1.0,以乙醇作溶剂,在回流温度下反应24 h,产率可达80%以上。合成C12-3(OH)-C12.2Cl的最佳条件为n(二甲基十二烷基叔胺)∶n(二甲基十二烷基叔胺盐酸盐)∶n(环氧氯丙烷)=2.0∶1.0∶1.0,以正丙醇为溶剂,在回流温度下反应3 h,产率可达94.5%以上。测定了它们的表面张力γ、临界胶束浓度cmc及降低水溶液表面张力的效率C20,结果表明:与相应的单头基单烷烃链表面活性剂相比,Gemini表面活性剂具有很低的cmc和很强的表面活性,联结基团对其性能有较大的影响。     

新型Gemini咪唑表面活性剂的合成与性能

以咪唑、溴代烷(1-溴十二烷、1-溴十四烷、1-溴十六烷)和2,2′-二氯二乙基醚为主要原料合成了3个新型Gemini咪唑表面活性剂,通过FT IR和~1H NMR对其结构进行了表征。根据表面张力和电导率考察了其表面性能,获取了一系列表面活性参数。结果表明,随着烷基链长的增加,表面活性剂的表面活性提高,同时表现出较高的乳化能力和泡沫能力。     

不同联接基的烷基咪唑表面活性剂的合成与表征

以咪唑和溴代十二烷为原料、1,2-二溴乙烷(1,4-二溴丁烷、对二溴苄)为联接基团,经两步反应合成标题化合物。利用IR、1HNMR对目标产物进行结构表征,并测定了目标产物的CMC、润湿性和泡沫稳定性。结果表明,合成的表面活性剂具有较低的CMC值,不同联接基团对CMC值影响不大,柔性联接基团的表面活性剂具有较好的润湿性和泡沫稳定性。     

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。     

可裂解Geminin型季铵盐表面活性剂的合成与性能

合成了一系列可裂解Gemini型季铵盐表面活性剂烷基-α,ω-双(二甲基酰氧乙基溴化铵),标记为Ⅱ-m-n(m=12,14;n=3,4,6);采用红外光谱和核磁共振进行结构表征.测定了相关的性能,结果表明,可裂解Gemini型季铵盐表面活性剂具有很强的胶束生成能力,其临界胶束浓度(CMC)为2.63×10-4～4.17×10-4mol/L(m=12)及2.88×10-5～4.46×10-5mol/L(m=14),分别比相应的单季铵盐表面活性剂的临界胶束浓度(CMC)低两个数量级;其泡沫稳定性、乳化性能和杀菌性明显优于相应的单季铵盐表面活性剂.     

不同结构的Gemini乳化剂对纳米苯乙烯-丙烯酸丁酯共聚物乳液性能的影响

采用自制的一系列含有不同联接基团的季铵盐型阳离子Gemini表面活性剂为乳化剂,制备了阳离子型纳米苯乙烯(St)-丙烯酸丁酯(BA)共聚物乳液,考察了3种Gemini表面活性剂及其用量对乳液形态结构及性能的影响,并提出了乳胶粒子的形成机理。结果表明,3种中间联接基团不同的Gemini表面活性剂(12-3-12、12-4-12、12-6-12)的临界胶束浓度(CMC)均比相应的单链表面活性剂十二烷基三甲基溴化铵低2个数量级,而这3种Gemini表面活性剂的CMC值相近;以3种Gemini表面活性剂作为乳化剂制备St-BA乳液具有很好的聚合稳定性,单体转化率高,乳液的总固物质量分数接近30%,乳胶粒子为球形,其粒径为50~66 nm,分布较窄;随着乳化剂12-3-12用量的增加,乳胶粒子粒径变化不大,分布较窄,凝胶量逐渐减小;当乳化剂用量为1.2 g时,乳液固含量和单体转化率最小,当乳化剂用量超过1.8 g时,乳液固含量和单体转化率变化不大;随着乳化剂12-4-12用量的增加,乳胶粒子粒径变化也不大,乳化剂对其他性能的影响规律与乳化剂12-3-12相同;随着乳化剂12-6-12用量的增加,乳液的凝胶量减小,固含量与单体转化率增加;含Gemini乳化剂的乳胶粒子是通过胶束成核形成的。     

Gemini表面活性剂与月桂醇醚羧酸盐的复配性能研究

研究了Gemini阳离子表面活性剂双十二烷基季铵盐(12-3(OH)-12)与阴离子表面活性剂月桂醇聚氧乙烯醚羧酸钠(AE9C)复配体系的稳定性、表面活性、泡沫性能、润湿性和乳化性能。结果表明,12-3(OH)-12与AE9C复配体系稳定性好,表现出很好的协调增效作用。当n(12-3(OH)-12)∶n(AE9C)=1∶2时,增效作用最为明显,其临界胶束浓度CMC为1.49 mmol/L,最低表面张力γCMC=30.15 m N/m,均低于任一单组分。复配体系的泡沫、润湿和乳化性能均要优于任一单组分,并且都在n(12-3(OH)-12)∶n(AE9C)=1∶2时表现出最佳性能。     

一种非对称双尾阳离子表面活性剂的合成及表面活性研究

以N,N-二甲基丙二胺、1-溴-十四烷、辛酸等为原料,通过酰化和季铵化反应合成了3个非对称双尾阳离子表面活性剂,用IR和1HNMR表征了中间体和目标产物。酰胺化反应的最佳条件为:投料比n(正辛酸)∶n(N,N-二甲基丙二胺)=1∶1.1,反应温度为120℃,反应时间为10 h。目标产物的最低表面张力(γCMC)均在20～30mN/m,临界胶束浓度(CMC)均在10-5～10-6 mol/L,γCMC和CMC均远低于结构类似单尾表面活性剂的γCMC和CMC。双尾阳离子表面活性剂的泡沫半衰期(T1/2)为22～31 min,泡沫稳定性强于单尾表面活性剂。     

烷基苯磺酸盐Gemini表面活性剂的结构与界面性质

以烷基酰氯为原料,经傅克酰基化反应、格林反应、催化氢化还原及磺化、中和等步骤,合成了10-4-10、12-4-12和10-6-10(10和12代表疏水基碳数,4和6代表连接基团碳数)3种不同结构的双烷基双苯双磺酸盐Gemini表面活性剂,并用核磁共振氢谱和电喷雾质谱对产物进行了结构鉴定。用旋滴法测定了其水溶液与正庚烷的界面张力,发现磺酸盐Gemini表面活性剂的CMC比对应的传统的表面活性剂的CMC低两个数量级,并且随着疏水基碳数或连接基团碳数的增加而降低。10-4-10、12-4-12和10-6-10的饱和吸附面积(Amin)分别为0.23、0.35和0.97 nm2,饱和吸附量(Γmax)分别为7.37×10-10、4.65×10-10和1.72×10-10mol/cm2,临界胶束浓度下的界面张力(γCMC)分别为3.60、3.06和1.89 mN/m。     

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。