新型防锈润滑添加剂的合成研究

以柠檬酸、壬基酚聚氧乙烯醚和二乙醇胺为原料合成了一种具有防锈、润滑双重功能的水基合成切削液添加剂———柠檬酸壬基酚聚氧乙烯醚单酯二乙醇酰胺。柠檬酸酐的制备条件为柠檬酸∶乙酸酐(摩尔比)为1.0∶1.2,温度为35℃,反应时间为18h;酯化摩尔比(酸酐∶OP)为1.0∶1.2,温度为80~90℃,反应时间为3h;酰胺化条件为柠檬酸壬基酚聚氧乙烯醚单酯∶二乙醇胺(摩尔比)为1∶1.5,反应温度为130~140℃,反应时间为3~4h。采用红外光谱法对产物进行表征,进而确定了合成的最佳工艺路线和工艺条件。     

琥珀酸十二醇聚氧乙烯醚单酯二乙醇酰胺合成与红外光谱表征

从顺丁烯二酸酐出发,经过单酯化、酰胺化等一系列过程,合成了一种具有防锈、润滑双重性能的水基合成切削液添加剂———琥珀酸十二醇聚氧乙烯醚单酯二乙醇酰胺。酯化条件为:酸酐/AEO9(物质的量比)1.0∶1.1,反应温度为85～95℃,反应时间为3～4 h;酰胺化条件为:琥珀酸十二醇聚氧乙烯醚单酯/二乙醇胺(摩尔比)为1∶1.2,反应温度为150～160℃,反应时间为2～3 h。采用红外光谱法对原料、中间体和产物进行表征,确定了合成的最佳工艺路线和工艺条件。     

壬基酚聚氧乙烯醚琥珀酸酯磺酸二钠盐的合成研究

以壬基酚聚氧乙烯醚,顺丁烯二酸酐亚硫酸钠为原料,合成了壬基酚聚氧乙烯醚琥珀酸酯磺酸二钠盐,探讨了反应温度和反应时间对其酯化反应和磺化反应的影响。     

OPS-1乳化剂的合成及应用

以壬基酚聚氧乙烯醚、顺丁烯二酸酐、无水亚硫酸钠为原料合成了壬基酚聚氧乙烯醚琥珀酸酯磺酸二钠盐,研究了反应温度和反应时间对酯化反应和磺化反应的影响,探讨了产品在乳液聚合等方面的应用     

壬基酚硫代物低聚体的研制

以壬基酚为主要原料,合成壬基酚硫代物低聚体。研究了反应温度、反应时间和物料比等因素对合成反应的影响。结果表明,合成壬基酚硫代物低聚体的最佳工艺条件为:在常压下,壬基酚与一氯化硫的物料比为2/1(摩尔比),反应时间为2h,反应温度为30℃。     

脂肪醇与烷基酚聚氧乙烯醚的改性研究

用脂肪醇聚氧乙烯醚和烷基酚聚氧乙烯醚与琥珀酸酐进行半酯化反应,合成二种新型混合离子型表面活性剂——壬基酚聚氧乙烯醚琥珀酸单酯(MPOENPS)和壬氧基聚氧乙烯琥珀酸单酯(MPOENS)。考察了在不同摩尔比条件下合成产物的表面活性,     

硫酸氢钠催化合成三苯乙烯苯酚聚氧乙烯醚油酸酯

以硫酸氢钠为催化剂,进行三苯乙烯苯酚聚氧乙烯醚和油酸的酯化反应,合成了三苯乙烯苯酚聚氧乙烯醚油酸酯,考察了酸醚摩尔比、催化剂用量、反应温度、反应时间等条件对酯化反应的影响。结果表明,较优的合成条件为:n(油酸)∶n(醚)=0.99∶1,催化剂用量为总反应物质量的0.50%,150℃回流反应5 h。在此条件下,酯化率达98%以上。     

硫酸氢钠催化合成三苯乙烯苯酚聚氧乙烯醚油酸酯

以硫酸氢钠为催化剂,进行三苯乙烯苯酚聚氧乙烯醚和油酸的酯化反应,合成了三苯乙烯苯酚聚氧乙烯醚油酸酯,考察了酸醚摩尔比、催化剂用量、反应温度、反应时间等条件对酯化反应的影响。结果表明,较优的合成条件为:n(油酸)∶n(醚)=0.99∶1,催化剂用量为总反应物质量的0.50%,150℃回流反应5 h。在此条件下,酯化率达98%以上。     

水乳剂用壬基酚聚氧乙烯配磷酸酯的合成

以壬基酚聚氧乙烯醚(TX-10)、P2O5为原料,合成了水乳剂壬基酚聚氧乙烯醚磷酸酯。通过对还原剂用量等因素的讨论,确定最佳工艺条件为:次亚磷酸钠用量为TX-10的0.4%,n(TX-10)∶n(P2O5)∶n(H2O)=2∶1∶0.8,反应温度60℃,反应时间5h。在此条件下产品的酯化率为96.84%。     

水杨酸甲酯的加压合成工艺研究

以水杨酸和甲醇为原料,对甲苯磺酸催化作用下合成了水杨酸甲酯,考察了酸醇摩尔比、反应温度、反应时间及反应压力对酯收率的影响。结果表明,较佳合成工艺条件为:n(水杨酸)∶n(甲醇)摩尔比=1∶5,反应温度120℃,反应时间5 h,反应压力162 kPa,在此条件下,酯收率接近90.0%。产品经FT-IR确定结构,用气相色谱检测,产品纯度达到99.5%。     

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.