极性单体就地增容PP／PA6共混物的研究

初步探索了采用极性单体马来酸二丁酯（ＤＢＭ）一步反应挤出就地增容ＰＰ／ＰＡ６共混物,结果表明：用ＤＢＭ一步法增容ＰＰ／ＰＡ６后,共混物的相容性得到改善,分散度增加,分散相畴尺寸减小,力学性能提高。ＤＢＭ用量和ＤＣＰ用量影响一步法的增容效果。     

尼龙6共混改性研究进展

系统介绍了国内外用聚乙烯、聚丙烯、PVDF、PAR、PET、PVOH、ABS、PC、PPO、SAN、弹性体、TLCP等改性尼龙 6的系列方法、研究成果及其性能 ,并提出了反应挤出共混改性和无机纳米材料改性尼龙 6的设想     

Compatibility of poly(vinylidene fluoride) (PVDF)/polyamide 12 (PA12) blends

Poly(vinylidene fluoride) (PVDF)/polyamide 12 (PA12) blends showed new peaks in XRD profile with increasing PA12 and the crystallinity of PA12 significantly decreased with the addition of PVDF. PVDF showed three relaxation regions at about −40, 40, and 100°C, respectively, and glass transition temperature (T_g ) of PA12 increased in blends (10.8→30.14°C) and α‐relaxation of PVDF decreased from 100.26 to 86.46°C. Complex viscosities (η*) vs. composition curve showed a great positive deviation in PVDF‐rich and a small negative deviation in PA12‐rich blends. The N—H and C=O stretching band of PA12 shifted slightly toward higher wavelength, and from curve‐fitted data the area of hydrogen‐bonded C=O stretching bands of PA12 decreased with the addition of PVDF, especially in the 30/70 blend, implying the existence of interactions between the β‐hydrogen atom of PVDF and amide carbonyl group of PA12 in the blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1374–1380, 2000     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Stable transfection of human β‐1,4N‐acetylgalactosaminyltransferase and α‐2,8‐sialyltransferase cDNAs in C6 rat glioma cells induces modifications in ganglioside metabolism

Ganglioside distribution in cells undergoes deep modifications during physiological and pathological events, possibly depending on the activity of glycosyltransferases involved in their biosynthesis. To understand how the ganglioside pattern can be altered by the selective expression of specific glycosyltransferases, C6 rat glioma cell line was stably transfected with two human glycosyltransferase cDNAs: β ‐1,4N‐acetylgalactosaminyltransferase (GalNAcT) and α ‐2,8‐sialyltransferase (ST‐II). GalNAcT and ST‐II are key enzymes in ganglioside biosynthesis; whereas ST‐II synthesizes GD₃, precursor of the “b” pathway, GalNAcT produces GM₂, GD₂ and asialo‐GM₂ and it is, therefore, involved in “a”, “b” and “asialo” pathways. C6 cells were subjected to three independent transfections: one with a construct containing GalNAcT cDNA, one with a construct containing the ST‐II cDNA, and one with both constructs simultaneously. Whereas control cells present mainly N‐acetyl‐ and N‐glycolyl‐GM₃, selected transfected clones show more complex ganglioside profiles: GalNAcT‐expressing cells are enriched in the “a” series gangliosides, ST‐II‐expressing cells synthesize the “b” series species, cells expressing contemporarily the two glycosyltransferases produce gangliosides of both series. Furthermore, among the selected clones, expression of GalNAcT and ST‐II correlates with changes in the ST‐I and ST‐IV activities, indicating that the switching on of the biosynthetic enzymes we investigated influences the activity of endogenous glycosyltransferases, possibly through the modification of the amount of their substrates or products.     

La(1−x)SrxCo1−yFeyO3 perovskites prepared by sol–gel method: Characterization and relationships with catalytic properties for total oxidation of toluene

La_(1−x)Sr_xCo_(1−y)Fe_yO₃ samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co₃O₄ that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La³⁺ by Sr²⁺ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La_0.7Sr_0.3Co_0.8Fe_0.2O₃. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O⁻ electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La³⁺ by Sr²⁺. The strong lowering of the temperature at conversion 20% for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O⁻ electrophilic species for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O⁻ species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe⁴⁺ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La_0.7Sr_0.3Co_0.8Fe_0.2O₃ sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co₃O₄ particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co₃O₄.     

聚氨酯结构对聚氨酯改性环氧树脂胶粘剂粘接性能的影响

合成了含不同硬段、软段及软段数均相对分子质量(M_n)的端异氰酸酯聚氨酯(IPTE),在一定条件下将其与环氧树脂E-51的仲羟基进行反应,制取聚氨酯(PU)改性环氧树脂(EP)。在相同固化条件下,测试了PU改性EP胶粘剂的剪切强度和剥离强度。研究结果表明,无论硬段是二苯基甲烷-4,4′-二异氰酸酯(MDI)还是甲苯二异氰酸酯(TDI),剥离强度均随着软段M_n的增加而增大,特别是当硬段为MDI时,剥离强度可分别增加2.4倍[软段为端羟基聚醚二元醇(PPG)]和6倍[软段为端羟基聚酯二元醇(PA)];而当PPG为软段时,剪切强度随着软段M_n的增加而逐渐降低;当PA为软段时,剪切强度随着软段M_n的增加呈先升后降的趋势,当M_n=1000时达到最大值。     

2-氯-6-甲基苯胺合成研究

提出以邻甲苯胺和尿素为起始原料,经缩合,得N,N＇-二（邻甲苯基）脲,再与氯磺酸与氨水反应在氨基对位形成磺酰胺阻塞基团,然后经脱碳酰基、氯化、水解脱阻塞基团,合成2-氯-6-甲基苯胺得到目标产物。首次报道了用二苯脲法保护氨基,用氯酸钠和浓盐酸代替双氧水和浓盐酸或氯气的氯化方法来合成2-氯-6-甲基苯胺。     

Electrochemical corrosion behavior of magnesium and titanium alloys in simulated body fluid

The electrochemical behavior of AZ91D and Ti–6Al–4V alloys was investigated in simulated body fluid (SBF) at 37 °C. The aim of the present study was to evaluate their corrosion performance through the analysis of corrosion resistance variation with time, using electrochemical impedance spectroscopy (EIS) tests and corrosion current density using potentiodynamic polarization measurements. Very low current density was obtained for Ti–6Al–4V alloy compared to that of AZ91D alloy, indicating a typical passive behavior for Ti alloy. EIS results exhibited high corrosion resistance indicating a highly stable film on titanium alloy compared to magnesium alloy in SBF.     

Ditopic, flexible hydrazone-based building blocks with pendant 2,2′:6′,2′′-terpyridine metal-binding domains

The synthesis and characterization of three new bis(2,2′:6′,2′-terpyridine) (tpy) ligands containing different hydrazone spacers between the metal-binding domains are described. Treatment of 1,4-benzenedicarbaldehyde bis(2,2′:6′,2′′-terpyridin-4′-ylhydrazone) (1) with [(tpy)RuCl₃] in the presence of N-ethylmorpholine results in the formation of [(tpy)Ru(μ-1)Ru(tpy)]⁴⁺. Single crystal X-ray diffraction data for [(tpy)Ru(μ-1)Ru(tpy)][PF₆]₄·8MeCN confirm the ability of the hydrazone-based ligand to bridge two ruthenium(II) centres, providing proof-of-principle for the application of this class of flexible ligand in the design of coordination polymers.