Neutral Pd(II) and Ni(II) Acetylide Catalysts for the Polymerization of Methyl Methacrylate

Homogenous polymerization of methyl methacrylate using Pd(II)- and Ni(II)-based acetylide complexes as initiators has been investigated. M(PR'₃)₂(CCR)₂ (M=Pd, Ni; R'=PPh₃, Pn-Bu₃; R=Ph, CH₂OH, CH₂OOCCH₃, CH₂OOCPh, CH₂OOCPhOH-o) were found to be a novel type of effective initiators for the polymerization of methyl methacrylate. Among them, Pd(C CPh)₂(PPh₃)₂ (PPP) shows the highest activity in the MMA polymerization and the PMMA obtained is a syndiotactic polymer with high number-average molecular weight (M _n) of 14.1 × 10⁴. Some features and kinetic behavior of MMA polymerization initiated by PPP were studied in detail. The polymerization reaction is first-order with respect to both [PPP] and [MMA]. Radical polymerization mechanism is proposed.     

沥青带水磺化工艺的研究

通过沥青磺化过程的主反应和副反应，进一步讨论了磺化工艺的原理，磺化试剂的选择，溶剂的组成，带水速度，溶剂的回收方式等各种因素对产品质量的影响。     

铝锆炭滑板在浇铸钙处理钢时的化学侵蚀

利用扫描电镜对抗钙处理钢液侵蚀试验后的铝锆炭残样进行了显微结构观察 ,并分析了铝锆炭滑板在钙处理钢液中的化学侵蚀机理。结果表明 :高温下 ,钙处理钢液中的Ca及CaO会与滑板中的Al2 O3 、SiO2 发生反应 ,生成低熔点的 12CaO·7SiO2 (1392℃ )和 2CaO·SiO2 ·Al2 O3 (15 39℃ )等物质 ,这些低熔物被钢水冲刷掉 ,使得滑板表层的Al2O3 和SiO2 含量迅速降低 ,从而导致了滑板的损毁。     

Preparation and characterization of sulfonated polyetherimide/polyetherimide blend membranes

Polyetherimide (PEI) was sulfonated by chlorosulfonic acid (CSA) in 1,2‐dichloroethane for the first time. With the increase of the CSA/PEI repeat unit ratio and/or reaction time, the ion‐exchange capacity (IEC) of the sulfonated polyetherimide (SPEI) increased accordingly. Water‐uptake testing and contact‐angle measurement showed that the hydrophilicity of the SPEI increases with the increase of the IEC. Membranes were fabricated from SPEI/PEI blends with different ratios. The morphologies of the blend membranes were examined by scanning electron microscopy, which showed that the membrane pore size is larger when SPEI with higher IEC was used. With the increase of SPEI ratio in the blend membranes, the membrane pore size also increased. The contact‐angle data of the membranes showed that the hydrophilicity of the blend membrane was elevated because of the sulfonate group on the SPEI molecular backbone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1709–1715, 2004     

Free radical grafting of glycidyl methacrylate onto polypropylene in a co-rotating twin screw extruder

Free radical grafting of glycidyl methacrylate (GMA) onto molten polypropylene (PP) was studied in a co-rotating twin screw extruder. Grafting yields of GMA obtained under various experimental conditions along the screw length allowed for a good appreciation of the effects of chemical parameters (the presence of styrene and the concentrations of peroxide and monomers) and those of processing parameters (feed rate, screw speed, and specific throughput). Similar to the results obtained in a batch mixer,¹ free radical grafting of GMA carried out in the extruder in the presence or absence of styrene proceeded rapidly, as it was virtually completed half-way down stream of the extruder. Additionally, the presence of styrene as a second monomer increased the GMA grafting yield reatly with reduced PP chain degradation. The ultimate GMA grafting yield increased with increasing concentration of peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene. This similarity between the batch mixer and the extruder is related to the fact that in both cases it is the concentration of the peroxide and its half lifetime that determine the grafting rate and the ultimate grafting yield. On the othe hand, the GMA grafting yield decreased with increasing screw speed or feed rate. For a particular specific throughput (the ratio of throughput to screw speed), an increase in throughput with a concomitant increase in screw speed brought about a decrease in GMA grafting yield. It was concluded that the GMA grafting yield is affected primarily by the residence time in the zone in which free radicals are not depleted. The effects of screw speed, feed rate, and specific throughput manifest mainly through this local residence time distribution. Specific energy is not a good measure of the performance of the extruder with respect to the free radical rafting of GMA onto PP. © 1995 John Wiley & Sons, Inc.     

Quaternary reactive dyes containing a thioether‐ethylsulphone group. Part 2; Application methods for the dyeing of nylon†

A member of the new series of cationic reactive dyes containing a thioether‐ethylsulphone grouping referred to in Part 1 of this series has been applied to nylon at pH 3–10. The dye is water soluble and shows excellent substantivity for nylon 6.6 when dyed at the boil at pH 8–10. Under alkaline conditions, gradual β‐elimination back to the vinylsulphone dye occurs and covalent bond formation quickly takes place with the fibre; the higher the pH the more rapidly this occurs. Dyeings carried out at pH 10 showed very good brightness and levelling, together with good wash fastness. The light fastness of dyeings at moderate depth was 4–5 on the Blue Wool scale.     

Ethanol electrooxidation on novel carbon supported Pt/SnOx/C catalysts with varied Pt:Sn ratio

Novel carbon supported Pt/SnO_x/C catalysts with Pt:Sn atomic ratios of 5:5, 6:4, 7:3 and 8:2 were prepared by a modified polyol method and characterized with respect to their structural properties (X-ray diffraction (XRD) and transmission electron microscopy (TEM)), chemical composition (XPS), their electrochemical properties (base voltammetry, CO_ad stripping) and their electrocatalytic activity and selectivity for ethanol oxidation (ethanol oxidation reaction (EOR)). The data show that the Pt/SnO_x/C catalysts are composed of Pt and tin oxide nanoparticles with an average Pt particle diameter of about 2 nm. The steady-state activity of the Pt/SnO_x/C catalysts towards the EOR decreases with tin content at room temperature, but increases at 80 °C. On all Pt/SnO_x/C catalysts, acetic acid and acetaldehyde represent dominant products, CO₂ formation contributes 1-3% for both potentiostatic and potentiodynamic reaction conditions. With increasing potential, the acetaldehyde yield decreases and the acetic acid yield increases. The apparent activation energies of the EOR increase with tin content (19-29 kJ mol⁻¹), but are lower than on Pt/C (32 kJ mol⁻¹). The somewhat better performance of the Pt/SnO_x/C catalysts compared to alloyed PtSn_x/C catalysts is attributed to the presence of both sufficiently large Pt ensembles for ethanol dehydrogenation and C-C bond splitting and of tin oxide for OH generation. Fuel cell measurements performed for comparison largely confirm the results obtained in model studies.     

Application of pulse discharge sintering (PDS) technique to rapid synthesis of Ti3SiC2 from Ti/Si/C powders

To synthesize Ti₃SiC₂ samples, pulse discharge sintering (PDS) technique was utilized to sinter elemental powders of Ti/Si/C with stoichiometric and off-stoichiometric ratios in a temperature range of 1200–1500 °C. The results showed that high purity Ti₃SiC₂ could not be obtained from the Ti/Si/C powder with molar ratio of 3:1:2, and Ti₃SiC₂ preferred to form at relatively low sintering temperature for a short time. When 5Ti/2Si/3C and 3Ti/1.5Si/2C powders were sintered for 15 min, the TiC content was respectively decreased to 6.4 and 10 wt.% at 1250–1300 °C. The corresponding relative density of the samples sintered from 5Ti/2Si/3C powder was calculated to be as high as 99% at the temperature above 1300 °C. It is suggested that low-temperature rapid synthesis of Ti₃SiC₂ would be possible through the PDS technique, provided that the composition of the starting powders should be adjusted to be off-stoichiometric ratio from 3:1:2.     

大直径浅圆仓缩尺模型试验研究

大直径浅圆仓在生产过程中,由于仓底的偏心卸料使筒仓仓壁产生不均受力,会给筒仓结构的使用带来安全隐患。通过对浅圆仓缩尺模型试验,模拟筒仓生产过程的卸料状况,并对筒仓仓壁及仓底廊道顶部进行压力测试,将测试结果与理论计算进行对比,从而得出偏心卸料与静载状态的超压系数,为大直径浅圆仓设计提供依据。     

国外聚甲醛生产技术现状与发展

综述了国外主要甲醛生产厂商的工艺技术，树脂生产技术的发展和品种开发情况。