活性炭负载Ti(SO_4)_2催化合成丙二酸二丁酯的研究

首次以活性炭负载硫酸钛 (Ti(SO4) 2 /C)作催化剂 ,合成丙二酸二丁酯 ,此催化剂活性高 ,选择性好 ,易分离 ,不腐蚀设备 ,反应时间短 ,是一种环境友好催化剂。考察了影响酯化反应的条件 ,获得优化工艺条件如下 :Ti(SO4) 2 负载量 2 0 % ,丙二酸 0 2mol,正丁醇 0 6mol,催化剂 0 8g ,反应温度 15 0℃ ,反应时间 90min ,丙二酸的转化率 94 %以上     

基于Pro/TOOLKIT异步模式特征识别方法

对Pro／Engineer（Pro／E）二次开发工具Pro／TOOLKIT（PTC公司为Pro／E软件提供的二次开发工具包）的异步模式进行了研究，充分利用参数化技术，开发了实体模型的特征识别系统。系统可以控制Pro／E的自动启动及关闭，使其在后台运行。通过模型的调用实现实体特征的快速识别提取，为模具估价系统的智能化设计做好了准备。     

Physical gelation of crystallizing metallocene and Ziegler-Natta ethylene-hexene copolymers

The effect of molecular architecture on the evolution of viscoelastic properties during crystallization was investigated using ethylene-hexene copolymers manufactured via metallocene (M-LLDPE) and Ziegler-Natta (ZN-LLDPE) processes. Differences in branching distribution were shown to have a drastic effect on the viscoelastic properties near the gel point. It is shown that the branching distribution rather than branch content is the determining parameter for the evolution of the rheological properties during isothermal and non-isothermal crystallization, and for the width of the solidification interval. We developed a partial melting technique for the preparation of stable critical gels of LLDPE whose viscoelastic properties correspond to the intermediate state between melt and solid. Local molecular conformation and crystallinity in these gels were characterized by Raman spectroscopy, which shows that the transition from melt-like to solid-like rheological behavior (physical gelation) in LLDPE occurs at a very low overall crystallinity of less than 5%.     

用CCD摄像法测量下喷环流反应器内的气泡行为

本文开发了一种集高速视频分析系统和计算机数字图像处理技术于一体的具有普适性的动态高速ＣＣＤ摄像系统，并利用该系统测定了两相三维下喷环流反应气内的环境气泡行为，考察了不同喷咀和操作条件对气泡行为及平均传质比表面积的影响。     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Dishwashing performance of mixed palm stearin sulfonated methyl esters and polyoxyethylene sorbitan esters

The detergency profiles of sodium salt α-sulfonated methyl esters derived from palm stearin (α-SMEPS) and polyoxyethylene (20) sorbitan monoesters (POESE) in mixed micelle systems were evaluated as a function of the weight ratios of α-SMEPS/POESE [polyoxyethylene (20) sorbitan monolaurate (12), polyoxyethylene (20) sorbitan monostearate (18∶0), and polyoxyethylene (20) sorbitan monooleate (18∶1)] at different water hardness values (5.12, 51.2, and 512.0 ppm CaCO₃) and temperatures (20, 30, 45, and 65°C), respectively. All the mixtures of α-SMEPS/POESE (12, 18∶0, and 18∶1) systems exhibited a synergistic effect at 65°C in the absence of hardness. This was evaluated by measuring the percentage of soil removed. The systems showed an increase in detergency with both the temperature and water hardness. Maximal detergency was observed with 5.12 ppm CaCO₃ in the mixed surfactant solution.     

Photocatalytic Activity of a TiO<Subscript>2</Subscript> Photocatalyst Doped with C<Superscript>4+</Superscript> and S<Superscript>4+</Superscript> Ions Having a Rutile Phase Under Visible Light

C⁴⁺ and S⁴⁺-codoped titanium dioxide (TiO₂) having a rutile phase was prepared. By doping C⁴⁺ and S⁴⁺ ions into a TiO₂ lattice, the absorption edge of rutile TiO₂ powder was largely shifted from 400 to 700 nm. 2-Methylpyridine and methyleneblue were photocatalytically oxidized at high efficiency on C⁴⁺ and S⁴⁺-doped TiO₂ under visible light at a wavelength longer than 5 nm.     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

Synthesis of Biodiesel from Canola Oil Using Heterogeneous Base Catalyst

A series of alkali metal (Li, Na, K) promoted alkali earth oxides (CaO, BaO, MgO), as well as K₂CO₃ supported on alumina (Al₂O₃), were prepared and used as catalysts for transesterification of canola oil with methanol. Four catalysts such as K₂CO₃/Al₂O₃ and alkali metal (Li, Na, K) promoted BaO were effective for transesterification with >85 wt% of methyl esters. ICP-MS analysis revealed that leaching of barium in ester phase was too high (~1,000 ppm) when BaO based catalysts were used. As barium is highly toxic, these catalysts were not used further for transesterification of canola oil. Optimization of reaction conditions such as molar ratio of alcohol to oil (6:1–12:1), reaction temperature (40–60 °C) and catalyst loading (1–3 wt%) was performed for most efficient and environmentally friendly K₂CO₃/Al₂O₃ catalyst to maximize ester yield using response surface methodology (RSM). The RSM suggested that a molar ratio of alcohol to oil 11.48:1, a reaction temperature of 60 °C, and catalyst loading 3.16 wt% were optimum for the production of ester from canola oil. The predicted value of ester yield was 96.3 wt% in 2 h, which was in agreement with the experimental results within 1.28%.