不同硬段含量聚天冬氨酸酯聚脲结构和性能研究

通过聚天冬氨酸酯、端氨基聚醚与脂肪族异氰酸酯六亚甲基二异氰酸酯三聚体/预聚物反应,合成了纯硬段聚脲和不同硬段含量的聚脲,并考察了硬段含量对聚脲的结构形态、动态力学性质和力学性质的影响。硬段含量为73%~50%的聚脲呈现微相分离的形态,随着硬段含量降低,软段和硬段相的混合程度提高,脲羰基的氢键化程度增加,NH基氢键键长增加,硬段玻璃化转变温度Tgh降低,软段玻璃化转变温度Tgs的变化幅度较小,微相分离程度降低。材料的拉伸强度、模量和硬度随着硬段增加而提高,弹性则随之降低。     

新型聚天冬氨酸酯聚脲的合成、结构与性能研究

通过二步法:(1) 4,4'-二氨基环己基甲烷(PACM)或3,3'-二甲基-4,4'-二氨基环己基甲烷(Laromin C260)与马来酸二乙酯的Michael加成反应,(2) 反应(1)产物与E-51环氧树脂的加成反应,合成了新型聚天冬氨酸酯(PAEs).与现有Michael加成法相比,二步法能明显缩短合成反应时间,更适合工业化生产.进一步通过PAEs与4,4'-二环已基甲烷二异氰酸酯(H12MDI)/聚四亚甲基二醇(PTMG)预聚物反应,常温合成了2种PAEs聚脲.采用FT-IR、1H-NMR和GPC等表征了PAEs,并采用FT-IR和DMA考察了PAEs聚脲的结构形态、反应活性和力学性质.研究结果表明,聚脲硬段氨基氢键化程度高,氢键键长为3.04 ?;脲羰基的氢键化程度分别为74.4%和73.2%,提高固化温度,有助于脲羰基氢键的形成.PAEs聚脲呈现微相分离的形态,是低活性、高强度的弹性体涂层材料.     

聚醚多元醇结晶性能对聚氨酯树脂氢键化及性能的影响

以异佛尔酮二异氰酸酯和异佛尔酮二胺为硬段,聚环氧丙烷醚二醇(PPG)和聚四亚甲基醚二醇(PTMEG)为软段,合成了系列聚氨酯(PU)树脂。采用傅里叶变换红外光谱仪和热重分析仪考察了软段的结晶性及硬段含量对PU树脂的氢键化程度、热稳定性能及拉伸性能的影响。结果表明:以非结晶型PPG为软段的PU树脂的总氢键化程度较高,而以结晶型PTMEG为软段的的PU树脂具有较高的热分解温度和拉伸强度;随硬段含量增加,PPG型及PTMEG型PU树脂的总氢键化程度无明显改变,但失重5%的温度分别降低了6.4,4.3℃,拉伸强度分别增大了8.30,22.64 MPa。     

异氰酸酯类型对热塑性聚氨酯弹性体性能的影响

分别以5种异氰酸酯为硬段,聚己二酸1,4-丁二醇酯二醇(PBA)为软段,制备了不同异氰酸酯型的热塑性聚氨酯弹性体(TPU)。通过傅里叶变换红外光谱(FTIR),差示扫描量热(DSC)和电子拉伸等测试对其结构和性能进行表征,探究了异氰酸酯类型对热塑性聚氨酯弹性体的软硬段相互作用、PBA结晶性和机械性能的影响。结果表明,HDI-TPU氨基氢键化程度最高,HMDI-TPU的硬段间氢键化程度、软段结晶度最高,IPDI-TPU的氢键化程度、软段结晶度最低。在制备的5种异氰酸酯型TPU中,HDI-TPU的拉伸强度为29.47 MPa,断裂伸长率874%,邵D硬度44,综合机械性能最佳。     

异氰酸酯类型对热塑性聚氨酯弹性体性能的影响

分别以5种异氰酸酯为硬段,聚己二酸1,4-丁二醇酯二醇(PBA)为软段,制备了不同异氰酸酯型的热塑性聚氨酯弹性体(TPU)。通过傅里叶变换红外光谱(FTIR),差示扫描量热(DSC)和电子拉伸等测试对其结构和性能进行表征,探究了异氰酸酯类型对热塑性聚氨酯弹性体的软硬段相互作用、PBA结晶性和机械性能的影响。结果表明,HDI-TPU氨基氢键化程度最高,HMDI-TPU的硬段间氢键化程度、软段结晶度最高,IPDI-TPU的氢键化程度、软段结晶度最低。在制备的5种异氰酸酯型TPU中,HDI-TPU的拉伸强度为29.47 MPa,断裂伸长率874%,邵D硬度44,综合机械性能最佳。     

氯水老化pH值对氨纶结构与性能的影响

为了研究氯水老化pH值对氨纶的影响,使用不同pH值的次氯酸钠溶液对氨纶进行老化处理,随后采用傅里叶变换红外光谱、X射线衍射、差示扫描量热及力学性能测试分析老化后样品的氢键化程度、微相分离程度、结晶性、热性能与拉伸性能。结果表明:氨纶氢键化程度、微相分离程度和硬段结晶度都随氯水p H值的降低而减弱。在热性能方面,随着氯水pH值的降低,氨纶的玻璃化转变温度与软段结晶熔融温度升高,软段结晶度减小。在拉伸力学性能方面,低pH值氯水处理后的氨纶表现出更小的断裂强力和断裂伸长率。     

硬段含量对MDI型热塑性聚氨酯性能的影响

以4,4'-二苯基甲烷二异氰酸酯(MDI)、聚四亚甲基醚二醇(PTMG)和1,3-丙二醇(PDO)为原料,采用预聚体法合成热塑性聚氨酯(TPU),利用FTIR、DSC及力学性能测试等手段探究了硬段含量对TPU性能的影响。结果表明,硬段含量增加,TPU的氢键化程度、玻璃化转变温度、硬段熔融温度、拉伸强度、撕裂强度、硬度和模量均随之增大,软段结晶熔融温度及断裂伸长率随之减小;在硬段质量分数33%～45%范围内,TPU呈现"海-岛"结构,且随硬段含量增加,微相分离程度逐渐增加。     

软段结构对脂肪族聚氨酯弹性体的结构与性能影响

分别采用聚丙二醇(PPG)、聚四氢呋喃二元醇(PTMG)、聚己二酸一缩二乙二醇三羟甲基丙烷酯多元醇(726)和聚己二酸新戊二醇酯二元醇(756)4种不同软段制备了基于异佛二酮二异氰酸酯(IPDI)的脂肪族聚氨酯弹性体(PUE),并通过FT-IR、DSC和TGA等表征了软段结构对PUE结构与性能的影响。结果表明,在相同硬段含量的条件下,PTMG制备的PUE具有最高的交联密度和最低的氨酯羰基氢键化程度。聚酯型PUE的耐热性和热氧老化性能均优于聚醚型PUE,由756合成的PUE具有最好的老化性能和热稳定性。     

软段分子量对氨纶的微相分离程度与拉伸性能的影响

分别采用分子量为1 400,1 800,2 200,2 600,3 000的不同聚四亚甲基醚二醇和4,4'–二苯基甲烷–二异氰酸酯反应,得到预聚体,用N,N–二甲基乙酰胺作为溶剂配制34.5%的预聚体溶液,后用乙二胺/丙二胺混合物扩链,制成纺丝原液。然后采用溶液干法纺丝得到5种氨纶样品,利用傅立叶变换红外光谱分析仪测试分析了上述样品的氢键化程度,再采用小角X射线系统和动态力学分析仪研究了软段分子量对氨纶的微相分离程度的影响,最后选择万能材料试验机测试其拉伸性能。结果表明:随着软段分子量增加,硬段含量减少,氨纶的氢键化程度、微相分离程度和断裂强力均为先增大后减小,在分子量为2 200时达到最大值;同时,断裂伸长率先减小后增大,在分子量为2 200时为最小值。     

甬道风量对干纺氨纶结构与性能的影响

采用聚四亚甲基醚二醇、4,4'–二苯基甲烷–二异氰酸酯、乙二胺、N,N–二甲基乙酰胺制成纺丝原液,分别在甬道风量为630,660,690,720,750 m3/h下制备了5种干纺氨纶。利用傅立叶变换红外光谱仪、X射线衍射测试仪、差示扫描量热仪、万能材料试验机研究了5种氨纶的氢键、热性能、结晶性以及拉伸性能。结果表明,随着甬道风量的增加,氨纶硬链段内部氢键化程度降低、结晶度降低,导致氨纶拉伸断裂强力降低;软链段局部取向程度降低、玻璃化转变温度降低,导致氨纶拉伸断裂伸长率增大。     

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.     

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.     

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.