氟硅阳离子表面活性剂的制备及性能

以含氢硅油(PMHS)、N-甲基-N-烯丙基-2-全氟-2-甲基-3-氧代己酰胺(NF2)、N,N-二甲基烯丙胺(DAEMA)为原料,在Karstedt催化剂作用下,经硅氢化反应后,再与CH3I进行季铵化反应,制备了氟硅阳离子表面活性剂(PF2DI);考察了温度、催化剂、反应物比例对硅氢化反应的影响;采用IR和19FNMR对产物结构进行了表征,并测定了产物分子量、阳离子活性物含量、溶解度、表面张力和润湿性能。得到较优硅氢化反应条件:n(Si—H)∶n(NF2)∶n(DAEMA)=10∶1∶9,2.5 g含氢硅油,120μL Karstedt催化剂(16.123 g Pt/L),80℃反应6 h,在该条件下转化率为58%。当n(Si—H)∶n(NF2)∶n(DAEMA)从10∶0.5∶9.5到10∶2∶8变化时,PF2DI的重均分子量Mw和数均分子量Mn、阳离子活性物含量、在水和乙醇中溶解度、临界胶束浓度(CMC)均逐渐减小;PF2DI水溶液的γCMC和在有机玻璃板及石蜡表面的接触角都先减小再增大;当n(Si—H)∶n(NF2)∶n(DAEMA)=10∶1∶9时,三者均达到最小值,此时PF2DI水溶液润湿性能最佳。     

N,N'-对苯二亚甲基-双(十二烷基二甲基氯化铵)/AEO9复配体系表面活性研究

以对二氯苄(XDC)和十二烷基二甲基叔胺为原料,合成了阳离子双子表面活性剂N,N'-对苯二亚甲基-双(十二烷基二甲基氯化铵)(XBDDMA)。产物结构经红外光谱(FT-IR)、核磁共振氢谱(~1H NMR)和碳谱(~(13)C NMR)进行了确认。研究了XBDDMA与脂肪醇聚氧乙烯(9)醚(AEO_9)按不同摩尔比复配所得体系的临界胶束浓度(cmc)、平衡表面张力(γ_(cmc))及动态表面张力。结果表明,当n(XBDDMA)∶n(AEO_9)=1∶9~9∶1时,随XBDDMA含量增加,复配体系的cmc先降低后升高,表面活性剂分子在表面上的极限占有面积(A_(min))持续降低,当n(XBDDMA)∶n(AEO_9)=1∶1时复配体系的cmc最小,为2.27×10~(-6)mol/L,γ_(cmc)也最小,为33.06 m N/m;XBDDMA的添加降低了吸附初期的扩散能,从而降低了AEO_9的动态表面活性,二者复配不具有动态表面活性的协同增效作用。     

一种含全氟壬烯基硅表面活性剂的制备

研究了2-甲基-2-全氟壬烯氧基乙氧基羰基乙基甲基二聚乙氧基硅烷(Ⅴ)的制备方法和表面活性。以甲基丙烯酸-2-全氟壬烯氧基乙基酯(Ⅰ)和甲基二氯硅烷(Ⅱ)为原料,在氯铂酸催化下经过硅氢化反应得到2-甲基-2-全氟壬烯氧基乙氧基羰基乙基甲基二氯硅烷(Ⅲ),Ⅲ与聚乙二醇(Ⅳ)缩合反应得到非离子表面活性剂Ⅴ。用FTIR和MS对其结构进行了表征,优化了硅氢化反应工艺条件,测试了Ⅴ水溶液的表面张力和临界胶束浓度(CMC)。中间体Ⅲ的较优合成条件为:以四氢呋喃为溶剂,n(Ⅰ)∶n(Ⅱ)=1∶1.2,50℃下反应24 h,收率68.0%。表面活性剂Ⅴ水溶液的临界胶束质量浓度为0.22 g/L,此时的表面张力为19.5 mN/m,表明Ⅴ是高活性氟硅表面活性剂。     

(3-脱氢枞酰氧基-2-羟基)丙基三甲基氯化铵的合成及其表面活性

通过脱氢枞酸钠(DHANa)和3-氯-2-羟丙基三甲基氯化铵(CTA)反应,以制备(3-脱氢枞酰氧基-2-羟基)丙基三甲基氯化铵(DHAHPTMC),考察了溶剂类型、反应温度和时间及物料比对产物收率的影响,用FTIR和~1H NMR表征了产物结构,表面张力法研究了产物的表面活性。实验结果表明,当CTA与DHANa物质的量比为3.0,异戊醇为反应溶剂,在回流条件下反应12.0h,DHAHPTMC的收率可达82%;研究结果还表明,DHAHPTMC的临界胶束浓度(cmc)为4.25×10~(-3)mol/L,cmc时对应的表面张力(γ_(cmc))为38.62 mN/m,能够实现的最低表面张力(γ_(min))在36.6mN/m左右。     

侧基聚醚/二苯甲酮紫外吸收基聚硅氧烷的合成与表征

以H2PtCl6.6H2O为催化剂,甲苯为溶剂,通过硅氢化反应将端烯丙基聚氧乙烯聚氧丙烯醚(F6)和紫外吸收剂4-(3-烯丙氧-2-羟基)丙氧基-2-羟基二苯甲酮(AHDBP)同时引入聚甲基含氢硅氧烷(PHMS),合成了侧基聚醚/二苯甲酮紫外吸收基聚硅氧烷(PE-PUVSi),并用IR、UV和1HNMR对产物结构进行了表征。结果表明,在反应温度为80℃~100℃,甲苯用量为m(甲苯)∶m(PHMS)=1∶1,n(C=C)∶n(Si-H)=1.23∶1,n(F6)∶n(AHDBP)=2∶1的条件下可得到具有良好水溶性和对波长为243.6 nm、289.2 nm、325.0 nm处的紫外光有强吸收作用的产物。     

微波辐射下一步法合成1-丁基-3-甲基咪唑六氟磷酸离子液体

采用微波辐射法一步合成1-丁基-3-甲基咪唑六氟磷酸([Bmim]PF6)离子液体,产物结构经过IR和1H NMR验证。通过考察各种影响因素对产物的影响得出最佳的反应条件:n(溴代正丁烷)∶n(1-甲基咪唑)∶n(六氟磷酸钾)=1.1∶1∶1.6(摩尔比),70℃以及250 W的微波功率下照射15 min,收率可达到92.7%。     

一种聚醚改性聚硅氧烷的合成与表征

以八甲基环四硅氧烷(D4)、四甲基环四硅氧烷(D4H)、六甲基二硅氧烷(MM)等为原料,经催化平衡化制备了一种低含氢量低分子量的侧链含氢硅油。在氯铂酸的催化下,制备的侧链含氢硅油与丙烯醇聚氧乙烯醚进行硅氢化加成,得到一种侧链聚醚改性聚硅氧烷。讨论了原料摩尔比、温度、催化剂浓度及反应时间对硅氢键转化率的影响。硅氢化反应最佳条件为:n(Si—H)∶n(CC)=1. 0∶1. 2,反应温度90℃,催化剂浓度13 mg/L,反应时间4 h。含氢硅油和产物的红外光谱进行了测试与解析,并测量了产物的粘度、浊点、表面张力等其它物化指标。     

一种氟硅表面活性剂的合成及其表面活性

研究了2-甲基-2-全氟-2'-甲基-3'-氧代己酰氧基乙氧基羰基乙基甲基二聚氧乙烯基硅烷(Ⅴ)的制备方法和表面活性。以甲基丙烯酸-2-全氟-2'-甲基-3'-氧代己酰氧基乙基酯(Ⅰ)和甲基二氯硅烷(Ⅱ)为原料,0.5%Karsted催化剂存在下(以Ⅰ的质量计),发生硅氢化反应,得到2-甲基-2-全氟-2'-甲基-3'-氧代己酰氧基乙氧基羰基乙基甲基二氯硅烷(Ⅲ)。Ⅲ与聚乙二醇(Ⅳ)缩合反应得到非离子表面活性剂Ⅴ。用FTIR和MS对其结构进行了表征,优化了硅氢化反应工艺条件,测试了Ⅴ溶液的表面张力、临界胶束浓度(CMC)和处理玻璃后的疏水性能。以四氢呋喃为溶剂,中间体Ⅲ的较优合成条件为:n(Ⅰ)∶n(Ⅱ)=1.2∶1,50℃下反应28 h,化合物Ⅱ的转化率可达到68.2%。表面活性剂Ⅴ水溶液的CMC为0.52 g/L,临界表面张力γ_(CMC)为22.8 m N/m,用V的THF溶液处理玻璃后,玻璃表面具有很好的疏水性和较好的疏油性。     

腰果酚季铵盐表面活性剂的合成与表面活性

以环氧氯丙烷和三甲胺制得活性中间体环氧丙基三甲基氯化铵(GTA),再将其和腰果酚进行反应得到了腰果基季铵盐表面活性剂(3-腰果酚氧基-2-羟基)丙基-N,N,N-三甲基氯化铵。采用IR和MS对产物结构进行了表征。通过单因素实验探索其较优合成工艺为:当GTA用量为0.05 mol时,溶剂乙醇用量30 mL,反应温度70℃,反应时间6 h,n(腰果酚)∶n(GTA)=1.2∶1,此条件下收率可达76.69%。采用表面张力法和电导率法分别测定了产品的临界胶束浓度(cmc),分别为6.38×10-3和6.36×10-3 mol·L-1,γcmc=38.86 mN·m-1。     

长链烷基改性有机硅聚醚共聚物的合成和应用性能研究

采用侧链含氢硅油、1-癸烯和烯丙基聚醚为主要原料通过硅氢加成反应,制备了一种长链烷基改性有机硅聚醚共聚物(PMGC)。利用IR和~1H NMR对产物的结构进行表征,并研究了含氢硅油的含氢量、黏度及1-癸烯与烯丙基聚醚的摩尔比对产品乳化能力、油脂兼容性及配方肤感的影响。研究表明,当含氢硅油的含氢量为0.4%,黏度为100 mPa·s,n(1-癸烯)∶n(烯丙基聚醚)=3∶1时,其乳化能力和油脂兼容性较佳,将其应用于BB霜配方中,滑感和滋润感较优。     

Sapindaceae,cyanolipids, and bugs

Scentless plant bugs (Heteroptera: Rhopalidae) are so named because adults of the Serinethinae have vestigial metathoracic scent glands. Serinethines are seed predators of Sapindales, especially Sapindaceae that produce toxic cyanolipids. In two serinethine species whose ranges extend into the southern United States,Jadera haematoloma andJ. sanguinolenta, sequestration of host cyanolipids as glucosides renders these gregarious, aposematic insects unpalatable to a variety of predators. The blood glucoside profile and cyanogenesis ofJadera varies depending on the cyanolipid chemistry of hosts, and adults and larvae fed golden rain tree seeds (Koelreuteria paniculata) excrete the volatile lactone, 4-methyl-2(5H)-furanone, to which they are attracted.Jadera fed balloon vine seeds (Cardiospermum spp.) do not excrete the attractive lactone. Loss of the usual heteropteran defensive glands in serinethines may have coevolved with host specificity on toxic plants, and the orientation ofJadera to a volatile excretory product could be an adaptive response to save time.Mention of a commercial product does not consititute an endorsement by the USDA.     

2008～2009年世界塑料工业进展

收集了2008年7月～2009年6月世界塑料工业的相关资料,介绍了2008～2009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、环氧树脂、不饱和聚酯树脂)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。     

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.     

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.     

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.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.