新疆夏子街钙基膨润土的高附加值开发

以新疆夏子街钙基膨润土为原料,进行了原矿湿法提纯、钠化改性及钠基土有机化改性及其应用研究.结果表明,湿法提纯前钙基膨润土的蒙脱石含量为91.79%,是一种高品位钙基膨润土,提纯后蒙脱石含量达到95.97%.钠化正交实验结果表明,NaF效果优于传统的钠化剂Na2CO3.在优化条件下钠化改性膨润土的阳离子交换容量(CEC)可达97.5 mmol/100g土,比原矿提高17.25 mmol/100g土.以钠化改性膨润土为原料制得的有机膨润土的粘度达到5.4 Pa*s.FTIR表明有机插层剂已进入膨润土的层间.XRD特征峰位移表明有机膨润土的层间距达到2.143 nm,比钙基膨润土层间距增加0.754 nm.SEM得到的结论与FTIR、XRD表征结果相吻合.将有机膨润土应用于涂料中,其各项检测指标均满足要求.有机膨润土对于金属离子废水的吸附效果优于钙基膨润土.由此可知新疆夏子街钙基膨润土的高附加值开发是可行的.     

新疆乌兰陵格膨润土的开发及性能表征

以新疆乌兰陵格膨润土为原料,进行了原矿湿法提纯、钙基膨润土钠化改型及钠基膨润土有机化改性用于钻井油基泥浆的研究.结果表明,湿法提纯前钠基膨润土的蒙脱石含量为57.55%;提纯后蒙脱石含量为60.91%.而钙基膨润土蒙脱石含量为56.53%,提纯后蒙脱石含量为59.48%.Na2CO3作为改型剂使钙基土的CEC(阳离子交换容量)提高了26.7%,钠化改型后所制得的有机土的粘度达到0.840Pa·s.季铵盐用量在(8.5～9.0)×10-4mol/g时,D1631有机土的粘度出现了明显的突变点.FTIR表明有机插层剂已进入膨润土的层间.XRD特征峰位移表明膨润土的层间距有明显增加.SEM观察也表明膨润土的层间距增大,层间厚度约为72nm.将有机膨润土应用于钻井油基泥浆中,各项指标均已达到要求,研究表明新疆乌兰陵格膨润土的高附加值开发是可行的.     

剥离型葡萄糖酸蒙脱石的制备及其表征

利用葡萄糖酸改性碱性钙基膨润土制备了一种与水溶性高分子材料亲合性较强的剥离型葡萄糖酸蒙脱石.通过单因素实验,分析了葡萄糖酸用量、反应温度、分散剂浓度等因素对葡萄糖酸蒙脱石剥离的影响,认为蒙脱石剥离可能是由于层间发生激烈的中和反应造成的.电子显微镜扫描表明这种剥离型蒙脱石为片状结构,纳米片的厚度为75～100 nm; DSC测定表明该葡萄糖酸蒙脱石的失水温度与葡萄糖酸钙相同,葡萄糖酸基团分布在纳米片的表面上;IR 扫描表明葡萄糖酸与蒙脱石的结合方式为化学键;XRD表征说明该葡萄糖酸蒙脱石仍为层状结构,为多层蒙脱石晶片组成.将该葡萄糖酸蒙脱石添加到木薯淀粉糊中,能使淀粉糊的黏性增加一倍.     

微波合成酚醛树脂/蒙脱石纳米复合材料结构的研究

在微波加热条件下制备酚醛树脂/有机改性蒙脱石纳米复合材料,研究了蒙脱石不同加入方法、不同加入量和搅拌时间对有机改性蒙脱石分散效果的影响,并用X射线小角衍射观测其微观结构。结果表明,苯酚和甲醛可以进入蒙脱石片层间进行缩聚反应,使蒙脱石片层间距扩大甚至剥离。     

钙基膨润土的有机改性及其结构表征

以钙基膨润土为原料,经提纯钠化改性,用十六烷基三甲基氯化铵对其进行有机改性。研究了改性剂用量、反应温度和反应时间对改性膨润土有机化程度的影响,得到了最佳实验条件：改性剂用量为35%（以钠基膨润土质量计）、反应温度为70 ℃、反应时间为2 h。利用红外光谱仪和X射线衍射仪对最优样品进行测试分析,结果表明：季铵盐插层进入了膨润土的晶层间,层间距明显增大,改性效果良好。     

层状双氢氧化物和蒙脱石的剥离及其自组装

以钙基蒙脱石为原料,氟化钠为钠化剂,十六烷基三甲基溴化铵为有机改性剂采用离子交换法制备了有机蒙脱石(CTA-MMT);以硝酸镁、硝酸铝、氢氧化钠和十二烷基磺酸钠为原料,采用水热法制备了有机型镁铝层状双氢氧化物(Mg Al-SDS-LDH);以氯仿为剥离介质,采用超声法剥离CTA-MMT和MgAl-SDS-LDH,分别获得了两种剥离型矿物溶胶,将其混合自组装制备了蒙脱石/层状双氢氧化物(MMT/LDH)组装材料。用XRD和AFM表征了CTA-MMT和MgAl-SDS-LDH及其剥离产物,并分析了组装材料的热稳定性。结果表明,CTA-MMT和MgAl-SDS-LDH在氯仿介质中剥离仅需20 min,剥离型CTA-MMT和MgAl-SDS-LDH片层平均厚度分别约为9和8 nm。MMT/LDH由剥离型CTA-MMT和MgAl-SDS-LDH片层有序组装而成,组装材料结构与MgAl-SDS-LDH和CTA-MMT的含量有关,其结构单元层间距2.59 nm(CTA-MMT含量较低时)随着组装材料中CTA-MMT含量的升高而转变为1.82 nm。MMT/LDH组装材料具有较单一的CTA-MMT或MgAl-SDS-LDH更高的热稳定性。     

马来酸酐改性蛭石的制备及表征

以有机小分子马来酸酐作为改性剂,利用球磨法在不同溶剂中对蛭石进行有机改性.对有机改性的蛭石进行了X射线粉晶衍射、Fourier变换红外光谱仪和热重分析表征.结果表明:在水溶液条件下,球磨能够使蛭石片层被马来酸酐分子剥离,蛭石的(001)面特征衍射峰消失.在有机溶剂中球磨,蛭石不能够被马来酸酐剥离.讨论了马来酸酐改性蛭石的机理.研究了球磨时间对马来酸酐改性蛭石的影响.     

钙钠基蒙脱石铝柱撑的制备和表征

以山西大同的钙钠基蒙脱石为原料,制备了铝柱撑蒙脱石.通过XRD,FT-IR,N2吸附-脱附等测试手段,分析了产物的层间距、比表面、孔特征和结构变化.结果表明:钙钠基蒙脱石铝柱撑能获得比较好的柱撑效果,层间距为1.94nm,BET比表面为273.87m2/g,微孔容积为0.1174cm3/g,微孔孔径的最可几分布为0.738nm,中孔孔径的最可几分布为3.766nm.     

抗高温白油基钻井液用有机土的研制及性能研究

通过对钙基膨润土钠化和有机改性,制备出了可抗240℃的白油基钻井液用有机土。测试表征及评价结果表明,改性后季铵盐类有机覆盖剂进入蒙脱石层间,在蒙脱石表面发生化学键连,晶层间距增大到18.78,有机土层片变得疏松;与国内外有机土相比,该有机土在白油中胶体率高,抗温性强,能起到很好的增粘提切和较好的流变性能,具有较好的推广前景。     

新型超分散有机蒙脱土的制备和表征

采用十六烷基三甲基溴化铵为插层剂,通过先机械搅拌后超声振荡的复合工艺对钠基蒙脱土进行了有机改性,制备了超分散蒙脱土并对其进行了表征.FTIR表明有机插层剂进入蒙脱土层间;XRD结果表明超分散蒙脱土层间距由改性前的1.01 nm增加到3.13 nm;SEM和TEM表明蒙脱土已被剥离成单个片层.粒径分析表明超分散蒙脱土有很好的亲油性和分散性;沉降对比实验说明超分散蒙脱土分散性好,可长时间悬浮在熔融己内酰胺中.     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

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.