季铵盐插层钠基蒙脱土的工艺研究

采用溴化十六碳烷基三甲铵对钠基蒙脱土进行改性,研究了反应温度、反应配比、反应时间和搅拌方式对蒙脱土插层效果的影响。FTIR证明有机插层剂已进入蒙脱土的层间;XRD结果表明蒙脱土的层间距由1．4nm增加到2．8～3．9nm;TEM观察表明蒙脱土的层间距增大。     

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.     

有机插层剂对聚酰胺6／MMT纳米复合材料制备的影响研究

以烷基胺、季铵盐和氨基酸作为有机插层剂与蒙脱土片层进行阳离子交换，制备出层间距不同的有机蒙脱土。采用熔融插层法和原位聚合法分别制备聚酰胺（R％）／蒙脱土（MMT）纳米复合材料，并利用XRD、FT-IR、TEM对有机蒙脱土及纳米复合材料进行结构表征。研究结果表明：用烷基胺、季铵盐和氨基酸有机插层剂改性的蒙脱土层间距由原来的1．25nm分别增大到3．21nm、3．99nm和1．82m；季铵盐有机插层剂更适用于熔融插层法制备PA6／MMT纳米复合材料，而氨基酸有机插层剂更适用于原位聚合法制备PA6／MMT纳米复合材料。     

新型有机蒙脱土的制备、结构表征及其分散性

采用十二烷基磺酸钠及十六烷基三甲基溴化铵对蒙脱土进行了一次、二次插层改性,红外光谱和X射线衍射表明,两种有机插层剂均已进入蒙脱土的层间,有机蒙脱土的层间距由1.22 nm增加到3.64nm;沉降实验结果表明这种改性蒙脱土在有机介质中表现出很好的分散性.     

有机蒙脱土的制备及表征

采用插层剂十六烷基三甲基溴化铵(1631-Br)与蒙脱土层问的阳离子进行交换,优化反应条件(插层剂用量、改性时间)分别制备了不同的有机蒙脱土并将其用X射线衍射,红外光谱和透射电镜进行测试,结果表明,加入饱和插层量25%的插层剂搅拌2 h即可制备能较大幅度改进高聚物与沥青相客性的有机蒙脱土材料.     

改性剂种类对蒙脱土结构和性能的影响

为增加蒙脱土(montmorillonite,MMT)和有机物的相容性和研究插层剂种类对MMT结构和性能的影响,采用Cu,Co和Ni无机金属阳离子,十二烷基磺酸钠、十二烷基硫酸钠、α-烯烃磺酸盐和十二烷基苯磺酸钠等有机阴离子表面活性剂及十六烷基氯化吡啶、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵等有机阳离子表面活性剂作为改性剂,对蒙脱土进行一次改性和二次改性,制备出一系列改性蒙脱土.研究了改性剂种类、插层方式、插层次序对插层效果的影响.X射线衍射分析表明:一次改性时,插层剂均能进入蒙脱土的层间,改性土的层间距由1.04nm增加到1.7～3.52nm;二次改性时,先阳离子后阴离子的插层顺序有利于层间距增大(4.14nm),还可利用配位作用将二次改性剂引入金属离子一次改性MMT中,使层间距增大.改性机理研究认为:阳离子改性机理为层间离子交换,而阴离子改性机理是改性剂和MMT表面形成了氢键.沉降实验表明一次改性土和二次改性土在有机溶剂中分散能力有所增强.     

天然钙蒙脱土的钠化改型和有机化改性

用碳酸钠作为钠化剂对天然钙蒙脱土进行了钠化改型,用CTAC、CTAB、C18三种插层剂分别对钠蒙脱土进行了有机插层改性。对钠化改型前后的蒙脱土进行了XRD、FTIR分析,对有机改性前后的蒙脱土用XRD、SEM、FTIR和TG-DTA等进行了表征和分析。结果表明:钙蒙脱土经钠化改型后,层间距增大,结晶度变差,活性增强;CTAC、CTAB、C18三种改性剂都能使蒙脱土的晶层间距有较大提高,其中,尤以C18改性剂的有机化效果最为显著;蒙脱土有机改性前后外观变化十分显著;有机改性蒙脱土的结构水无明显变化,层间吸附水显著减少,疏水的有机插层剂主要进入蒙脱土层间,大量脱去层间吸附的水分子,对晶体结构本身并无影响。有机改性后,蒙脱土的吸附水与层间水的脱水温度与脱水量均显著降低,有机插层剂的大量插入,改变了原土的亲水性使之变为疏水,并提高了其热稳定性。     

聚乳酸／有机蒙脱土纳米复合材料的制备及结构表征

采用二次插层法制备了CTAB2-Cu1-MMT(依次采用铜离子和十六烷基三甲基溴化铵改性后的蒙脱土),其层间距由1.415 nm扩大到3.244 nm.利用丙交酯和二次插层的蒙脱土采用原位聚合法制备了聚乳酸/有机蒙脱土纳米复合材料.采用红外、热分析、粉晶衍射等方法对复合材料进行表征,研究了蒙脱土的加入量对复合材料结构、热稳定性的影响.结果表明:聚乳酸插入到蒙脱土层间,其起始热分解温度由70℃提高到240℃,热稳定性能得到改善.     

羟基铁柱撑剂性能对柱撑蒙脱土层间距的影响

考察柱撑蒙脱土层间距与羟基铁在制备及插层过程性能的关系,测定羟基铁插层蒙脱土过程溶液电导的变化规律;研究老化时间对羟基铁柱撑剂的粒度、电导及所制得的柱撑蒙脱土层间距的影响;碱化剂加入量对羟基铁柱撑剂粒度及所制得的柱撑蒙脱土层间距的影响.实验结果表明蒙脱土达到饱和吸附所需羟基铁柱撑剂的加入量为铁离子毫摩尔数与蒙脱土克数之比等于10;采用碱化剂加入量Na2CO3/Fe(NO3)3摩尔比等于0.5制备羟基铁柱撑剂插层蒙脱土,可制得层间距较大的柱撑蒙脱土;老化时间为4天的羟基铁柱撑剂插层蒙脱土能得到晶体比较规整的羟基铁柱撑蒙脱土.由实验数据分析可知,柱撑蒙脱土层间距的尺寸大小与柱撑剂的粒度及荷电性能有关.     

三聚阳离子表面活性剂改性蒙脱土的制备与表征

合成了一种含六氢三嗪的新型三聚季铵盐阳离子表面活性剂T16,以13C NMR和ESI-MS表征其结构,并作为有机插层剂应用于蒙脱土的改性。红外光谱(FTIR)、热重分析(TGA)表明,T16已插层到蒙脱土片层间。X射线粉末衍射(XRD)表明,T16改性后蒙脱土层间距从原来的1.486 nm增加到3.324 nm。沉降实验表明,改性后蒙脱土在苯乙烯和甲苯中形成凝胶体系,表现出很好的相容性和分散性,有利于聚合物或其单体进入蒙脱土层间形成纳米复合材料。     

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.