丁二酸酐酯化改性糯米淀粉的研究

目的 为了提高糯米淀粉的粘度，以达到标签胶的要求。方法 对糯米淀粉进行丁二酸酐酯化改性，通过单因素试验及响应面优化确定出最佳酯化条件，测定其理化性质，并对其进行结构表征。结果 丁二酸酐酯化改性糯米淀粉的最优工艺条件：丁二酸酐添加量（丁二酸酐占淀粉干基的质量百分比）为10.3%，酯化温度为41.5℃，酯化时间为2.0 h,pH为9.0，在此条件下制得的糯米淀粉胶的粘度较高，可达到61.6 Pa·s，且溶解性与溶胀度均有不同程度的提高。电镜与热力学性质分析表明，酯化后淀粉颗粒结晶结构受到破坏，表面粗糙，出现凹陷与裂缝。结论 经过丁二酸酐酯化后，糯米淀粉胶的粘度得到提高。     

Alkoxyl side-chain effects of acidic ionic liquids catalysts for the esterification of n-butyl butyrate

Three kinds of alkoxy group-functionalized acidic ionic liquids (ILs) are reported in this work, namely, 1-(methoxyethyl)-3-methylimidazolium hydrogen sulphate [MOE-MIM]HSO₄, 1-(ethyoxyethyl)-3-methylimidazolium hydrogen sulphate [EOE-MIM]HSO₄, and 1-(propyoxyethyl)-3-methylimidazolium hydrogen sulphate [POE-MIM]HSO₄. The short side chain on the cation of [MOE-MIM]HSO₄ decreases the solubility of the IL in butanol and butyric acid and facilitates the separation of the IL from a reaction medium. The yield of butyl butyrate is up to 99.5%. After 10 rounds of recycling, the catalytic performance of [MOE-MIM]HSO₄ shows no significant changes.     

白藜芦醇丙烯酸酯的合成及抗氧化活性研究

以白藜芦醇为先导化合物,合成了白藜芦醇丙烯酸酯,以获得具有更好抗氧化活性的白藜芦醇衍生物。以白藜芦醇和丙烯酰氯为原料,酯化法得到白藜芦醇丙烯酸酯。以维生素C为阳性对照,研究白藜芦醇丙烯酸酯对2,2-联苯-1-苯基肼(DPPH)自由基的清除活性和抗氧化活性。用NMR和HRLC-MS对白藜芦醇丙烯酸酯进行了表征。目标产物白藜芦醇丙烯酸酯收率为30.2%。白藜芦醇丙烯酸酯的抗氧化活性高于白藜芦醇,但低于维生素C。合成得到了白藜芦醇丙烯酸酯,其反应路线简单易行,条件温和,产物抗氧化活性较先导化合物有所提高。     

H3PW12O40/酸改性硅藻土催化剂的制备、表征及催化合成乙酸正丁酯

以硫酸改性后的硅藻土为载体，Keggin结构磷钨酸为活性组分，通过浸渍法制备出负载型催化剂H₃PW₁₂O₄₀/改性硅藻土，并对催化剂进行傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、扫描电镜（SEM）、X射线能谱（EDS）和N₂-程序升温脱附（N₂-TPD）表征。结果表明：酸改性后硅藻土的微孔增大增多，比表面积增大。H₃PW₁₂O₄₀均匀分布在改性硅藻土载体上，负载后磷钨酸仍保持Keggin结构。以H₃PW₁₂O₄₀/改性硅藻土为催化剂催化乙酸和正丁醇液相合成乙酸正丁酯，通过正交试验探索优化工艺条件。在较优工艺条件下，即w(40%H₃PW₁₂O₄₀/改性硅藻土)=1.1%（基于反应物质量），n(酸)∶n(醇)=1∶3，125℃反应2.0h，酯化率高达98.1%。催化剂重复催化使用5次，酯化率仍可达86.1%。H₃PW₁₂O₄₀/改性硅藻土可作为催化合成乙酸正丁酯的高效催化剂，具有活性高、用量少、价格低廉、制备简单、后处理简便、无废液排放等优点。     

Cross-linking of cellulose and poly(ethylene glycol) with citric acid

A novel approach to modifying native cellulosic fibres with poly(ethylene glycol) (PEG) impregnation and simultaneous cross-linking by citric acid (CA) was investigated. To understand the contributions of different components in the system, control references with just CA and cellulosic fibres (filter paper) were studied. The effect of sodium hypophosphite as a catalyst was also assessed. The results revealed that ester bonds are indeed formed in the cellulose–PEG–CA reaction system, as indicated by weight percentage gain (WPG) and FTIR analysis. The best results were achieved by using 5% CA and 10% PEG (calculated as weight-% from cellulose). In the reaction, the environmentally friendly CA prevents PEG from being leached out of cellulose during washing, resulting in promising future applications in dimensionally stabilized products based on cellulosic fibres.     

白藜芦醇磺酸酯的合成及抗氧化、抗肿瘤活性的研究

以白藜芦醇和2, 4-二硝基苯磺酰氯为原料,通过酯化法得到白藜芦醇磺酸酯,通过NMR和LC-MS确定了该化合物结构。以维生素C为阳性对照,研究白藜芦醇磺酸酯对2, 2-联苯基-1-苦基肼(DPPH)自由基和2, 2′-联氮-双-3-乙基苯并噻唑啉-6-磺酸(ABTS)自由基的清除活性和抗氧化活性;噻唑蓝(MTT)法研究其对人肺癌细胞A549的增殖活性。实验结果表明,目标产物收率为33.1%。同时,目标产物在浓度为1.0 mg/mL时,对DPPH自由基和ABTS自由基的清除率分别为31.6%和42.7%,抗氧化活性均高于白藜芦醇,但低于维生素C;目标产物对人肺癌细胞A549具有较好抑制作用,IC50值为(10.2±0.37)μg/mL。     

原油及馏分油脱酸技术进展

石油酸是原油和馏分油中普遍存在的腐蚀性物质，其主要成分为环烷酸并且含量可以高达90%以上。环烷酸具有羧酸的所有化学性质，所以常常造成严重的腐蚀，从而影响原油加工设备及油品使用设备的正常运行和使用寿命。随着近年来世界范围内高酸原油产量的逐渐增加，高原油及各种高酸值馏分油所带来的腐蚀与产品质量问题显得愈发严重，因此迫切需要开发出经济高效的脱酸技术与工艺路线。本文较为全面而详细地总结并评述了国内外原油及油品的各种脱酸技术方法。分析表明：目前所报道的各类脱酸工艺较多，其中工业应用的加氢脱酸效果虽好但是成本较高，而其他大多数脱酸方法都存在较多的缺点或不足，因此探寻一种绿色环保、经济高效并且具有较好普适性的油品脱酸工艺显得非常迫切而必要。酯化法脱酸具有加工工艺简单、不需要复杂的后继处理，几乎可以降低所有的高酸值原油和油品（轻质、重质馏分油以及渣油）的酸值，为原料油的进一步加工提供了方便。酯化脱酸工艺的关键在于高效催化剂的选择，而目前的催化酯化体系虽然脱酸率较高，但仍存在着反应时间较长的不足，相信通过反应过程强化等手段解决该问题以后，催化酯化脱酸工艺会被很快投入到原油及油品的脱酸实际工业生产中去。     

Microwave-assisted catalytic synthesis of phytosterol esters

A low-temperature reaction is of considerable importance in avoiding the degradation of phytosterol esters caused by high temperatures. In this study, an efficient method under mild conditions was developed to synthesise phytosterol esters by using microwave-assisted catalyst dodecyl benzene sulphonic acid (DBSA). The phytosterol conversion reached 94.27% under the optimal conditions: oleic acid to phytosterol molar ratio of 2.5:1, catalyst dosage of 20% (mol%) and reaction temperature of 60°C for 60 min. Fourier transform infrared (FTIR) spectroscopy was applied to determine the structure of phytosterol oleates. Moreover, a second-order kinetic model describing phytosterols esterification exhibited an adequate agreement with the experimental data. Microwave irradiation achieved the reduction of energy barrier (Ea = 29.17 kJ mol⁻¹) in comparison with conventional heating (Ea = 49.22 kJ mol⁻¹). This study suggests that microwave-assisted catalyst DBSA is a reliable and efficient method for the production of high-quality phytosterol esters.