微波诱导稀土固体超强酸SO4^2-／TiO2／Ce^4＋催化合成乙酸正丁酯

本文探讨了标题合成方法中合成反应条件对酯收率的影响。其最佳反应条件为：n(醇)：n(酸)=2．5：1．0，固体超强酸用量为反应物总质量的2．0％，微波辐射功率528W，辐射时间20min，酯收率达89．5％。用IR等手段对产品进行了确证。     

Influence of Distributed Particle Size on the Determination of the Parabolic Rate Constant for Oxidation by the Powder Method

The established analysis for the study of oxidation using powder specimens is based on the assumption of monosized particles. The experiments, however, are conducted on powders with a distributed particle size. Here we present a statistical approach for the calculation of the rate constant for oxidation. The results of the analysis are applied to new data on oxidation studies of dense powders of silicon carbonitride amorphous ceramics. The monosized model requires a wide range of values for the rate constant to fit the short term and the long-term data, leading to considerable ambiguity in the estimate of the parabolic rate constant, k _p, for oxidation. In contrast the statistical model fits over the entire range of data, yielding a much more reliable value for k _p. For example, the monosized approach gave a value in the range 19.7 × 10⁻¹⁸ < k _p < 2.7 × 10⁻¹⁸ m²/s. In contrast, the statistical model yields a specific value of 4.5 × 10⁻¹⁸ m²/s.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Mechanical properties of poly(lactic acid) and wheat starch blends with methylenediphenyl diisocyanate

Poly(lactic acid) (PLA) and wheat starch are biodegradable polymers derived from renewable sources. A previous study showed that thermally blending starch and PLA in the presence of methylenediphenyl diisocyanate (MDI) enhanced the mechanical properties of the blends. In this work, blends of PLA with various levels of wheat starch and MDI were hot mixed at 180°C then hot‐pressure molded at 175°C to form test specimens. The blends were characterized for mechanical properties, fracture microstructure, and water absorption. Pure PLA had a tensile strength of 62.7 MPa and elongation of 6.5%. The blend with 45% wheat starch and 0.5 wt % MDI gave the highest tensile strength of about 68 MPa with about 5.1% elongation. The blend with 20% starch and 0.5 wt % MDI had the lowest tensile strength of about 58 MPa with about 5.6% elongation. Dynamic mechanical analysis showed that storage modulus increased and tan δ decreased as starch level increased, but almost leveled off when starch level reached 45% or higher. Water absorption of the blends increased significantly with starch content. Yet the blend, if water proofed on its surface, has potential for short‐term disposable applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1257–1262, 2002; DOI 10.1002/app.10457     

A new class of corrosion inhibitors for waterborne coatings: 4-methyl-γ-oxo-benzene-butanoic acid complexes

Amine and transition metal based complexes with 4-methyl-γ-oxo-benzene-butanoic acid represent a new class of corrosion inhibitors specifically designed for long-term corrosion protection in waterborne coatings. Today, corrosion protection in waterborne technology is typically achieved using traditional anticorrosive pigments initially developed for use in solventborne coatings. Regulations concerning heavy metals and limitations regarding the compatibility and performance of such materials in waterborne coatings have created a need for novel approaches. Mechanistic aspects are discussed for the 4-methyl-γ-oxo-benzene-butanoic complexes based on electrochemical solution experiments (electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV)) and investigations performed on coated substrates. Exposure results underline the high efficiency of such complexes for both long-term corrosion protection and weld seam rust control in waterborne coatings.     

PTA生产降低醋酸单耗的技术

影响醋酸单耗的主要因素是醋酸损失,装置负荷以及系统中Na+的多少。减少醋酸损失的措施为①氧化反应温度190℃左右;②薄膜蒸发器下料的温度为165～180℃;③溶剂脱水塔的回流比为3.2～3.4,回流温度为80～95℃;④高压吸收塔洗涤水的用量为2t/h。装置应尽量在满足负荷或超负荷条件下运行,清洗碱液要排尽并用水彻底冲洗,减少Na+进入系统以此来降低醋酸单耗。     

丙烯腈装置副产氢氰酸的工业利用

氢氰酸是丙烯腈的副产品，综合利用氢氰酸将会提高丙烯腈装置的经济效益。介绍了几种利用氢氰酸合成其它化学品的工业生产方法，旨在使企业更多地了解氢氰酸的综合利用。     

Chemical analysis of volatiles emitted by Pinus svlvestris after induction by insect oviposition

Gas chromatography – mass spectrometry analyses of the headspace volatiles of Scots pine (Pinus sylvestris) induced by egg deposition of the sawfly Diprion pini were conducted. The odor blend of systemically oviposition-induced pine twigs, attractive for the eulophid egg parasitoid Chrysonotomyia ruforum, was compared to volatiles released by damaged pine twigs (control) that are not attractive for the parasitoid. The mechanical damage inflicted to the control twigs mimicked the damage by a sawfly female prior to egg deposition. The odor blend released by oviposition-induced pine twigs consisted of numerous mono- and sesquiterpenes, which all were also present in the headspace of the artificially damaged control twigs. A quantitative comparison of the volatiles from oviposition-induced twigs and controls revealed that only the amounts of (E)--farnesene were significantly higher in the volatile blend of the oviposition-induced twigs. Volatiles from pine twigs treated with jasmonic acid (JA) also attract the egg parasitoid. No qualitative differences were detected when comparing the composition of the headspace of JA-treated pine twigs with the volatile blend of untreated control twigs. JA-treated pine twigs released significantly higher amounts of (E)--farnesene. However, the JA treatment induced a significant increase of the amount of further terpenoid components. The release of terpenoids by pine after wounding, egg deposition, and JA treatment is discussed with special respect to (E)--farnesene.     

敌敌畏敌百虫清洁生产工艺

敌敌畏、敌百虫系中毒高效农药,仍保持着旺盛的市场前景。对敌敌畏敌百虫的传统生产工艺和“一步法”合成工艺进行了比较,后者产品含量高,质量稳定,对环境污染小,属清洁生产工艺。     

Controller design for nonlinear systems using the Contoured Robust Controller Bode plot

In this paper, we develop the Contoured Robust Controller Bode (CRCBode) plot and demonstrate its use in the design of robust controllers for nonlinear single‐input single‐output (SISO) systems. The CRCBode plot shows contours (level sets) of a robust performance quantity on the Bode magnitude and phase plots of the controller. An iterative frequency domain loop‐shaping design approach is employed to eliminate all intersections of the controller frequency response with certain ‘forbidden regions,’ indicating that a standard SISO robust stability and performance criterion is satisfied. Nonlinearities are accounted for by avoiding the maximum forbidden regions over a structured uncertainty set consisting of linearizations of the system dynamics about several operating points. We demonstrate this technique by designing and experimentally verifying a flow‐rate controller for a butterfly‐valve based liquid cooling system, which is robust to valve nonlinearities and flow disturbances. Finally, we compare this compensator with one generated using an automated H _∞ synthesis algorithm and discuss the advantages of the CRCBode approach. Copyright © 2013 John Wiley & Sons, Ltd.