双恶唑啉及环氧类扩链剂对TPEE的改性研究

采用恶唑啉类扩链剂和环氧类扩链剂对热塑性聚酯弹性体(TPEE)进行扩链反应,并对扩链产物的特性黏度、熔融指数和力学性能等进行测试和表征,考察了两类扩链剂对TPEE性能的影响,结果表明:在实验范围内当双恶唑啉类扩链剂加入量为0.7%,环氧类扩链剂加入量为0.9%时,所得TPEE的力学性能最好;环氧类扩链剂对TPEE的扩链效果优于双恶唑啉类。     

双恶唑啉对尼龙6改性作用的研究

以双恶唑啉为扩链剂,通过熔融挤出对尼龙6进行改性作用的研究.结果表明:双恶唑啉的用量存在最佳值,用量不足时偶联反应不充分,用量过多时封端反应加剧.扩链剂用量为最佳值时,扩链后尼龙6的特性黏度从0.96 dL/g增加到1.17 dL/g,端羧基含量和熔体指数分别降低为初始值的20%和38%.差式扫描量热分析表明:扩链后的尼龙6结晶度降低,扩链后尼龙6的缺口冲击强度有所提高.     

熔融反应扩链制备高黏度PA6及其力学性能研究

采用熔融反应挤出作为聚酰胺6(PA6)的扩链方法,以不同马来酸酐含量的苯乙烯-马来酸酐共聚物(SMA)为扩链剂,对PA6进行了扩链研究。对扩链后产物的特性黏度、熔体质量流动速率、氨基含量、凝胶含量及力学性能进行了表征。结果表明,马来酸酐摩尔分数为50%的SMA对PA6扩链效果较好,可使其特性黏度由2.0dL/g增大至4.2 dL/g,熔体质量流动速率则从115 g/10min减小至0.5 g/10min;通过扩链后的PA6氨基滴定测试表明,SMA在熔融挤出过程中与PA6末端氨基官能团进行反应从而引发PA6扩链。经扩链改性,PA6的力学性能得到明显改善,拉伸强度由62 MPa提高至85 MPa,缺口冲击强度则从3.8 kJ/m2提高至7.5 kJ/m2。     

环氧类扩链剂制备高黏度尼龙6及其性能表征

采用化学扩链的方法,将环氧类扩链剂与尼龙(PA)6通过双螺杆挤出机进行熔融反应,制备高黏度PA6,并对扩链后的PA6特性黏度、力学性能和流变行为进行了研究。结果表明,扩链剂的加入提高了PA6的特性黏度、力学性能和平衡扭矩,同时降低了熔体流动速率(MFR)。但扩链剂用量存在一个最佳值,当扩链剂质量分数为0.9%时,扩链后的PA6特性黏度、缺口冲击强度、拉伸强度、断裂伸长率、弯曲强度、弯曲弹性模量和平衡扭矩均达到最大,相对于纯PA6分别提高了86.25%,30.59%,21.44%,275%,19.08%,15%和132%,而MFR最低,较纯PA6降低了73.33%。     

扩链改性对聚对苯二甲酸乙二酯挤出吹膜成型的影响

通过添加多官能团环氧扩链剂对聚对苯二甲酸乙二酯(PET)进行扩链改性,然后用改性PET进行吹膜成型,研究了扩链剂含量对PET特性黏度、膜泡稳定性及薄膜力学性能和透明度的影响。结果表明,扩链剂的添加显著提升了PET的特性黏度;随着扩链剂含量的增加,薄膜膜泡稳定性以及表面质量、最大吹胀比、拉伸强度得到显著改善,断裂伸长率呈先增大后减小的趋势。当扩链剂质量分数为0.7%时,PET的特性黏度由纯PET的0.71 d L/g上升至0.94 d L/g,最大吹胀比则由1.9提高至4.5,横纵向拉伸强度分别为61.7 MPa和64.4 MPa,横纵向断裂伸长率达到最高,分别为12%和12.45%,较扩链剂质量分数为0.2%时提高了105.5%以及125.1%,而透光率仅下降1.4%,得到了性能较优的吹塑薄膜制品。     

亚磷酸三苯酯对r-PETG扩链反应和力学性能的影响

采用亚磷酸三苯酯(TPPi)为扩链剂,通过扩链反应来提高回收的共聚酯(r-PETG)的分子量,增加其特性黏度。采用凝胶渗透色谱(GPC)、熔融指数仪和红外光谱(IR)考察了TPPi的用量、扩链反应温度和混炼转速对r-PETG扩链反应的影响。在最佳反应条件(TPPi为2.0%、温度200℃、转速60 r/min)下,r-PETG的熔体流动速率(MFR)由12.83 g/10 min降低到4.24 g/10min;数均分子量(M_n)由2.52×10~4g/mol提高到3.35×10~4g/mol,提高了33.3%;拉伸强度从41.2 MPa增加到了62.3 MPa;而无缺口冲击强度从38.4 k J/m~2大幅度提高至66.8 k J/m~2。红外光谱证实了扩链反应前、后r-PETG的分子结构没有变化。     

扩链剂联用对PETG扩链反应与流变性能的影响

通过扩链反应对聚对苯二甲酸乙二醇1,4环己烷二甲醇酯（PETG）进行改性以提高PETG的熔体强度和黏度。采用熔体流动速率仪、旋转流变仪及转矩流变仪考查了扩链剂的使用方式对PETG结构及流变性能的影响。结果表明,酸酐类和环氧类多官能团单体联用对PETG的扩链效果最好,PETG的熔体流动速率由12.83 g/10 min降低至7.50 g/10 min,零剪切黏度（η0）由2022.8 Pa·s增加到4764.2 Pa·s,特征松弛时间（τ0）由0.78 s增加到3.58 s;改性后PETG仍保持着线形结构而未形成凝胶。     

PA6/MGF复合材料的力学及摩擦学性能

用硅烷偶联剂KH550和二苯甲烷二异氰酸酯(MDI)分别对磨细玻璃纤维(MGF)进行表面改性(即KMGF,M-MGF),采用熔融法制备PA6/MGF复合材料。实验结果表明:PA6/M-MGF复合材料中M-MGF质量分数为20%时,拉伸强度从65.82 MPa提高到71.78 MPa,缺口冲击强度从11.86 k J/m2提高到23.73 k J/m2,增强增韧作用优于PA6/K-MGF复合材料;摩擦磨损性能研究发现,PA6/M-MGF复合材料的摩擦因数随着M-MGF质量分数的增加而下降;PA6/M-MGF和PA6/K-MGF复合材料的磨损率的变化趋势一致。     

助剂复配对聚乙醇酸性能的影响

通过熔融共混方法,采用环氧类扩链剂对聚乙醇酸(PGA)进行反应挤出改性,同时添加亚磷酸酯类抗氧剂来降低熔融加工过程中的热降解。研究了扩链剂与抗氧剂联用对PGA熔体质量流动速率、热稳定性、熔体流变性能以及抗水解性能的影响。结果表明,扩链剂与抗氧剂复配,PGA改性料的熔体质量流动速率由原料的44.2 g/10min下降至11.2 g/10min;起始分解温度T_-5%(质量剩余95%的温度点)提高22.1℃;熔体黏度提高6倍以上;在提高了熔体强度的同时,改性料热稳定性明显改善,同时抗水解稳定性也有一定程度提高。     

采用双螺杆反应挤出提高PA 66的熔体黏度

采用双螺杆反应挤出的方法研究了双环氧宫能团化合物扩链剂(EP)对聚酰胺(PA)66的扩链效果。研究发现:随着EP含量的增加,PA 66的黏度也随之提高,当w(EP)达到1.8%时,体系黏度达到最大值;当w(EP)超过2.0%时,体系开始出现凝胶。扩链后PA 66的相对分子质量提高,因此力学性能明显提高,尤其是悬臂梁缺口冲击强度和断裂伸长率提高的幅度较大,分别为63%,100%。     

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.     

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.     

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.     

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.