壳聚糖基固体酸催化果糖合成5-羟甲基糠醛

以壳聚糖为原料,采用一步水热碳化和磺化法合成壳聚糖基固体酸材料(CASA),并将其用于催化无溶剂条件下果糖脱水合成5-羟甲基糠醛(5-HMF),考察了催化剂用量、反应温度、反应时间及催化剂循环利用次数对脱水反应的影响,并与甲壳素基固体酸材料(CISA)进行了催化性能比较。采用X射线衍射、扫描电镜、吡啶吸附红外光谱对CASA材料进行了结构和酸性质表征,建立了催化剂结构与性能的关系。结果表明,CASA材料含有大量的表面强Br?nsted酸性位点,因而其催化性能较CISA突出;当m(果糖)∶m(CASA)=6∶1、120℃反应5 h时,5-HMF的收率高达63.2%,且CASA可重复利用4次而无明显失活。     

日本酱油与中国酱油在不同模拟条件下挥发性呈香物质分析

采用无溶剂萃取检测,结合主成分分析（PCA）法,研究中日酱油在模拟蘸料和炒菜条件下挥发性呈香物质的差异,确定出典型呈香物质,为快速区分中日酱油的风味提供参考。结果显示：在模拟蘸料条件（25 ℃）下,检测到日本酱油呈香酯类物质居多,其含量约是中国酱油的2倍;中国酱油呈香吡嗪类物质居多,是日本酱油的1.6倍。在模拟炒菜条件（95 ℃）下,日本酱油呈香物质种类增加35%,中国酱油增加59%,约是日本酱油的1.7倍。日本酱油中醇类、酯类和醛类物质表现突出,乙醇为日本酱油的典型呈香物质,赋予其浓厚醇香;中国酱油中吡嗪类、酯类和酮类物质占比较大,赋予其浓郁酱香,苯乙醇为中国酱油的典型呈香物质,赋予一定的花香和果香。     

油管内壁耐温耐磨涂层材料的研制及性能研究

针对我国油气传输管道在高温高压(150~200℃,34~36 MPa)服役条件下的磨损腐蚀问题,以无溶剂环氧树脂体系为基础,通过固化剂及填料筛选、配方正交设计及黏度影响因素研究,研制了适用于油管内壁综合性能良好的耐温耐磨涂层材料。涂层采用固化反应温度更高以及力学性能更好的0421型固化剂,选择碳化硅、碳纤维和聚四氟乙烯作为填料,研究不同粒径的填料所制备涂层的力学性能和黏度,发现当碳化硅粒径为18μm,碳纤维粒径为75μm时,涂层力学性能更佳且黏度更低,同时通过正交试验确定了碳化硅、碳纤维和聚四氟乙烯的最佳用量分别为占树脂总量的30%、10%、5%,并在涂料体系黏度影响因素研究中发现聚四氟乙烯对体系的黏度影响最大。以上述试验为基础,最终研制出的涂料及涂层各项性能达到技术指标要求。     

Optimization of citrus peels D-limonene extraction using solvent-free microwave green technology

Attention is presently drawn to the development of a new and green alternative technique for the extraction of essential oil from citrus plant materials. This study was aimed at the extracting essential oil from orange and lemon peels using solvent-free microwave method. This process uses microwave-assisted hydro-diffusion technique to extract essential oil from citrus peels. Response surface methodology was used to investigate the effect of microwave power (200–1,000?W) and extraction time (10–40?min) on the essential oil yield. The oil extracted was characterized using Fourier transform infrared radiation (FTIR) and Gas chromatography–mass spectrometry analysis to determine the functional groups and chemical components present, respectively. The optimum yield of extract from orange and lemon peels were 3.7 and 2.0%, respectively at corresponding power of 1,000?W and time of 10?min. The analysis of variance results showed that the resulting models for both orange and lemon peels were significant and microwave power had greater influence on the extraction processes at both linear and quadratic levels. The FTIR analysis revealed prominent functional groups of alkenes that majorly constitute limonene compound at 1,642 and 1,643?cm^?1 for orange and lemon peels, respectively. The present process permits fast and efficient extraction, avoids water and solvent consumption, and allows substantial energy savings.     

Solvent-free enzymatic synthesis of structured lipids from peanut oil and caprylic acid in a stirred tank batch reactor

Structured lipids were synthesized by transesterification of peanut oil and caprylic acid in a stirred-batch reactor. Different substrate molar ratios (1:1 to 1:4, peanut oil/caprylic acid) were used. The reaction was performed for 72 h at 50°C catalyzed by IM60 lipase from Rhizomucor miehei (10 g, 2% w/w substrate) in the absence of organic solvent. The highest incorporation of caprylic acid was obtained with a 1:2 molar ratio (peanut oil/caprylic acid) after 72 h reaction. With a 1:2 molar ratio, the incorporation increased by 28% from 1:1. On the other hand, a 1:4 molar ratio gave the lowest incorporation during the reaction. The effect of different mixing speeds (200, 640, or 750 rpm) on reaction was studied with a 1:2 substrate molar ratio for 24 h. A high incorporation of caprylic acid (14.3 mol%) was obtained at 640 rpm, while 200 rpm gave the lowest incorporation (2.2 mol%), suggesting that good mixing is essential in a stirred-batch reactor. After 24 h of reaction at different rpm, IM60 lipase was recovered, washed with hexane, and reacted with substrates to study its stability after reaction at different mixing speeds. The results showed that caprylic acid incorporation was similar (24.9, 24.3, 24.2 mol%) at 200, 640, and 750 rpm, respectively. When 20 g of IM60 lipase (4% w/w substrate) instead of 10 g was used in a 1:1 substrate molar ratio reaction, the incorporation of caprylic acid increased by 26% after 72 h. To study enzyme reuse, 10 g of IM60 lipase was used in a 1:1 substrate molar ratio for 24 h at 640 rpm. The incorporation of caprylic acid gradually decreased with increased number of reuses. During five times of reuse, 15, 13.9, 9.6, 6.7, and 9.7 mol% of caprylic acid were incorporated into peanut oil, respectively.     

混合多元醇对无溶剂聚氨酯覆膜胶性能的影响

以聚己二酸-1,4-丁二醇酯(PBA)、植物油多元醇、异弗尔酮二异氰酸酯(IPDI)和小分子多元醇为主要原料,制备了一种双组分无溶剂型聚氨酯胶粘剂。研究了双组分的配比R′和混合多元醇组分对聚氨酯胶粘剂固化速率、固化后胶膜的热稳定性和吸水率的影响,并测试了覆膜样品的T剥离强度。结果表明:当双组分配比R′=1.3时,胶粘剂综合性能最佳;添加小分子多元醇并不能提高胶粘剂的固化速率和耐热性,但能显著改善胶粘剂的粘结性能,并且选择性添加适量的小分子二醇,还能增强其耐水性。     

Zinc-Imidazolate Films as an All-Dry Resist Technology

Motivated by the drawbacks of solution phase processing, an all-dry resist formation process is presented that utilizes amorphous zinc-imidazolate (aZnMIm) films deposited by atomic/molecular layer deposition (ALD/MLD), patterned with electron beam lithography (EBL), and developed by novel low temperature (120 °C) gas phase etching using 1,1,1,5,5,5-hexafluoroacetylacetone (hfacH) to achieve well-resolved 22 nm lines with a pitch of 30 nm. The effects of electron beam irradiation on the chemical structure and hfacH etch resistance of aZnMIm films are investigated, and it is found that electron irradiation degrades the 2-methylimidazolate ligands and transforms aZnMIm into a more dense material that is resistant to etching by hfacH and has a C:N:Zn ratio effectively identical to that of unmodified aZnMIm. These findings showcase the potential for aZnMIm films to function in a dry resist technology. Sensitivity, contrast, and critical dimensions of the patterns are determined to be 37 mC cm⁻², 0.87, and 29 nm, respectively, for aZnMIm deposited on silicon substrates and patterned at 30 keV. This work introduces a new direction for solvent-free resist processing, offering the prospect of scalable, high-resolution patterning techniques for advanced semiconductor fabrication processes.     

无溶剂环氧涂料的抗阴极剥离性能

研究了环氧涂层抗阴极剥离性能的主要影响因素,结果表明,涂料自身性能、表面处理状况以及阴极保护电位均对涂层的抗阴极剥离性能产生影响。     

甲基有机硅树脂的无溶剂合成研究

以甲基三乙氧基硅烷单体和二甲基二乙氧基硅烷单体为原料,采用水解-缩聚的方法合成了甲基有机硅树脂,并研究了无溶剂合成甲基有机硅树脂的条件。结果表明,一定配比,水解温度为70℃,缩聚温度为80～85℃,反应时间为4h,可合成无溶剂体系的甲基有机硅树脂;红外光谱(IR)表明,合成的甲基有机硅树脂在Si-O-Si处有较宽的吸收峰;固化温度为140℃,固化4h,得到无色透明甲基有机硅树脂。     

选择性催化加氢合成氯代苯胺最新进展

如何抑制脱氯氢解副反应是实现高效绿色合成氯代芳胺的核心问题。依据氯代硝基苯催化加氢合成氯代苯胺反应的抑制脱氯方法,选择性加氢催化剂设计思路可分为调变催化剂金属组分与载体的相互作用,制备双/多金属催化剂、非晶态合金催化剂、聚合物稳定的贵金属催化剂和杂原子修饰的贵金属催化剂等。本文分别综述了近年来各类抑制脱氯方法的研究进展及抑制脱氯机理,并进一步分析比较了不同反应介质对催化反应性能的影响。现有研究表明,杂原子修饰的贵金属催化剂表现出更好的催化性能,无溶剂条件下合成氯代苯胺彰显了绿色友好化工理念。两者有望成为今后的研究热点。