疏水缔合聚合物驱乳状液破乳规律研究

本文采用瓶试法考察了直链型、支链型及超支化型聚醚破乳剂及其与阳离子反相破乳剂协同作用对乳状液破乳效果的影响。结果表明,超支化聚酰胺-胺聚醚破乳剂与阳离子反相破乳剂协同作用对模拟疏水缔合聚合物驱乳状液有良好的破乳效果,随着聚醚破乳剂分子结构中环氧乙烷(EO)数增加,破乳效果增强,破乳剂最佳的EO/PO质量比为1/1。聚酰胺-胺聚醚破乳剂能显著降低油水之间的界面张力和界面扩张模量,表明该破乳剂分子易于在油水界面吸附,并破坏原乳状液界面膜的强度,从而有利于破乳。     

改性含氟聚醚稠油破乳剂的合成与性能评价

为解决稠油破乳困难问题,以3,4,5-三氟苯酚、甲醛等为原料合成起始剂,以KOH为催化剂,与环氧乙烷(EO)、环氧丙烷(PO)进行聚合反应生成含氟苯酚酚胺树脂聚醚,利用2,4-甲苯二异氰酸酯对聚醚进行交联改性,合成了一类改性含氟聚醚破乳剂,分析了不同破乳剂的浊点、亲水亲油平衡(HLB)值、相对溶解度(RSN)及表面张力值,考察了破乳剂浓度、温度对破乳性能的影响,得到了最佳破乳条件。结果表明,起始剂与PO质量比为1∶159,PO与EO质量比为3∶1时所合成的经改性后的MF-06破乳剂破乳效果最佳。在150min内,破乳剂浓度为90mg·L~(-1),温度为70℃时,MF-06破乳剂对辽河油田稠油采出液的脱水率为94.6%,油水界面分离清晰整齐,优于OX-932和SP169。     

茶多酚胺型嵌段聚醚破乳剂合成及性能研究

以茶多酚胺型酚醛树脂为起始剂,与EO、PO通过缩合反应合成一类新型茶多酚胺型嵌段聚醚破乳剂。采用FTIR对起始剂的分子结构进行了表征,通过瓶试法研究了对塔里木油田、克拉玛依油田、辽河油田、大庆油田采出液的破乳性能。实验结果表明,所合成的新型破乳剂具有良好的破乳脱水性能,且广谱性强。在破乳温度为50℃,破乳剂加剂量为80 mg/L,破乳时间为120 min时,最高脱水率均在85%以上,且油水界面整齐,脱出水清澈、脱盐效果显著,显示出良好的应用前景。     

茶多酚胺型嵌段聚醚破乳剂合成及性能研究

以茶多酚胺型酚醛树脂为起始剂,与EO、PO通过缩合反应合成一类新型茶多酚胺型嵌段聚醚破乳剂。采用FTIR对起始剂的分子结构进行了表征,通过瓶试法研究了对塔里木油田、克拉玛依油田、辽河油田、大庆油田采出液的破乳性能。实验结果表明,所合成的新型破乳剂具有良好的破乳脱水性能,且广谱性强。在破乳温度为50℃,破乳剂加剂量为80 mg/L,破乳时间为120 min时,最高脱水率均在85%以上,且油水界面整齐,脱出水清澈、脱盐效果显著,显示出良好的应用前景。     

聚醚型原油破乳剂结构与破乳性能关系的研究

以直链和支链结构的醇类、胺类以及稠环树脂为起始剂,通过烷氧基化反应合成了一系列嵌段聚醚型破乳剂。针对新疆塔河油田原油,讨论了聚醚破乳剂的起始剂类型、支化结构、起始剂含量、环氧乙烷与环氧丙烷质量比值[m(EO)/m(PO)]以及嵌段结构和方式对其脱水效果的影响。结果表明,针对新疆塔河油田原油,合成的多分枝型聚醚破乳剂脱水效果较好;聚醚破乳剂的起始剂质量比在0.3%～1.5%,HLB值在9.5～11.5,破乳脱水效果较好;末端为PEO嵌段的二嵌段聚醚破乳剂脱水速率快,脱水率最高;多嵌段结构聚醚破乳剂脱水速度较慢,但分离出的水色清,污水含油率低。     

基于环氧树脂交联复配的破乳剂性能评价

在稠油乳状液的处理领域,化学破乳已经被广泛应用。对四种交联环氧乙烷(EO)和环氧丙烷(PO)破乳的剂性能进行了研究。通过对破乳剂脱水效率测定,界面张力的动态测量等实验,结果表明交联破乳剂的性能与其主体化学结构、环氧支链数直接相关,双亲性嵌段共聚破乳剂在提高脱水效率的同时,对乳状液的界面张力、屈服应力均会有显著影响,随着破乳剂用量加大,乳状液中胶质与水分的比重升高,部分乳状液中的基团开始聚集,限制乳状液中液滴的流动,利于破乳效率的提高。     

酚胺醛树脂破乳剂的合成与性能研究

针对新疆高含水原油的特性,制备了非离子型双酚A酚胺醛树脂嵌段聚醚破乳剂(BPAE)。酚胺醛树脂起始剂的合成工艺为双酚A、甲醛和二乙烯三胺按1∶4∶6的反应摩尔比例,在70℃、N2环境下充分反应1 h,再在120~220℃下减压蒸馏得到酚胺醛树脂起始剂。将上述酚胺醛树脂作为起始剂依次与PO、EO进行开环聚合反应合成BPAE。通过热化学瓶试法,比较了BPAE、腰果酚胺醛树脂破乳剂(CPAE)、壬基酚胺醛树脂破乳剂(NPAE)、SP169在不同破乳剂加剂量、破乳温度、破乳时间对原油脱水的影响。通过这几种聚醚破乳剂的破乳脱水实验表明,胺基改性酚醛树脂嵌段聚醚的破乳效果很好,其中BPAE破乳效果最优。在破乳剂浓度为25 mg/L、破乳温度40℃、破乳时间为120 min条件下,原油脱水率可达85.4%。     

腰果酚醛树脂嵌段聚醚的合成及其破乳性能研究

以腰果酚和甲醛为原料合成一种起始剂——腰果酚醛树脂,再以起始剂为原料,分别与环氧丙烷(PO)和环氧乙烷(EO)进行加成聚合,合成了一种腰果酚醛树脂嵌段聚醚(CPFE)。采用FT-IR对CPFE的分子结构进行了表征,通过瓶试法初步研究了CPFE作为破乳剂对大庆油田采出液的破乳性能。实验结果表明,所合成的CPFE对O/W型原油乳液具有良好的破乳性能,随着添加量和破乳温度的增加,脱水率增大,所表现出来的影响规律与常规聚醚型破乳剂是一致的。在破乳温度为45℃,CPFE的添加量为250mg/L时,30min的脱水率达到97.8%,腰果酚醛树脂嵌段聚醚具有快速脱水的特征,显示出良好的应用前景。     

酚胺醛树脂破乳剂的合成与性能研究

针对新疆高含水原油的特性,制备了非离子型双酚A酚胺醛树脂嵌段聚醚破乳剂(BPAE)。酚胺醛树脂起始剂的合成工艺为双酚A、甲醛和二乙烯三胺按1∶4∶6的反应摩尔比例,在70℃、N2环境下充分反应1 h,再在120²20℃下减压蒸馏得到酚胺醛树脂起始剂。将上述酚胺醛树脂作为起始剂依次与PO、EO进行开环聚合反应合成BPAE。通过热化学瓶试法,比较了BPAE、腰果酚胺醛树脂破乳剂(CPAE)、壬基酚胺醛树脂破乳剂(NPAE)、SP169在不同破乳剂加剂量、破乳温度、破乳时间对原油脱水的影响。通过这几种聚醚破乳剂的破乳脱水实验表明,胺基改性酚醛树脂嵌段聚醚的破乳效果很好,其中BPAE破乳效果最优。在破乳剂浓度为25 mg/L、破乳温度40℃、破乳时间为120 min条件下,原油脱水率可达85.4%。     

对叔丁基酚胺醛树脂型破乳剂的制备

选取对叔丁基苯酚、甲醛、二乙烯三胺为原料合成对叔丁基酚胺醛树脂作为起始剂,KOH为催化剂,通过与环氧乙烷(EO)、环氧丙烷(PO)加成反应合成对叔丁基酚胺醛树脂型嵌段聚醚破乳剂。性能优良破乳剂的关键为起始剂的制备,本实验通过单因素法确定合成的工艺条件为:对叔丁基苯酚∶甲醛∶二乙烯三胺=1∶0.8∶0.8(摩尔比),反应温度为95℃,反应时间为180 min。利用红外光谱、核磁共振氢谱对起始剂的结构进行表征。结果表明,起始剂为目标产物。对叔丁基酚胺醛树脂型破乳剂对辽河老化油脱水实验结果表明,破乳剂脱水速率快,脱水率较高,且油水界面清晰整齐,能够达到老化油工业化处理的应用条件。     

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.     

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.     

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.