巯基-苯基聚倍半硅氧烷的合成

以巯丙基三甲氧基硅烷和苯基三甲氧基硅烷为原料,在甲醇作溶剂、浓HCl作催化剂的条件下水解缩合制备了巯基聚倍半硅氧烷和巯基-苯基聚倍半硅氧烷,并利用FTIR和GPC对合成产物进行了表征。结果表明:当苯基单体添加量为20%时,所制备的巯基-苯基聚倍半硅氧烷中均含有一定量的巯基和苯基,在引入部分苯环增加折光率的同时也保持了产物拥有进一步反应的活性巯基,且相对分子质量较大,分子量分布较窄。     

梯形聚甲基/苯基倍半硅氧烷的合成及其热稳定性研究

选用甲基三氯硅烷和苯基三氯硅烷为主要原料合成了梯形聚甲基倍半硅氧烷(有机硅树脂Ⅰ)和梯形聚苯基倍半硅氧烷(有机硅树脂Ⅱ).并进行了红外光谱和差热分析.     

二步法合成乙烯基八聚笼型倍半硅氧烷

采用正硅酸乙酯和四甲基氢氧化铵为原材料,合成了八聚四甲基铵基笼型倍半硅氧烷;采用二甲基乙烯基氯硅烷对其进行乙烯基取代,得到含乙烯基的八聚笼型倍半硅氧烷。采用核磁共振硅谱29Si-NMR、红外光谱IR和凝胶渗透色谱GPC对其结构进行了分析。     

八氯甲基笼型倍半硅氧烷的合成及表征

以氯甲基三氯硅烷为原料,甲醇、氯仿和石油醚为混合溶剂,在浓盐酸和无水三氯化铁为催化剂的条件下水解缩合制备了八氯甲基笼型倍半硅氧烷(CM-POSS)。利用FT-IR、GPC、1 H-NMR、29Si-NMR和XRD等技术对产物的结构进行了表征,并通过TGA研究了其热稳定性。结果表明产物为八氯甲基笼型倍半硅氧烷,且热稳定性良好。     

POSS对壳聚糖膜的阻湿与拉伸性能的影响

目的研究以四甲基铵基笼形聚倍半硅氧烷(Octa TMA POSS)为填料,制备壳聚糖基复合膜,对壳聚糖薄膜的水蒸气阻隔性能和力学性能进行改善。方法采用溶液共混流延法制备复合膜,测定其水蒸气透过系数、表面接触角、溶胀度、溶解度、吸附等温曲线、拉伸性能、成膜液流变性能、微观形貌和X射线衍射等。结果笼形聚倍半硅氧烷的加入可提高复合膜对水分子的阻隔性,尤其是质量分数为3%时,其水蒸气透过系数下降了15.9%。同时,壳聚糖薄膜的力学性能也得到改善,在质量分数低于5%时,壳聚糖薄膜的抗拉强度、弹性模量可同时得到提高。结论四甲基铵基笼形聚倍半硅氧烷的加入可改善壳聚糖薄膜的阻湿性能和力学性能,可大大提升其在食品包装领域的应用潜力。     

离子液体中淀粉颗粒接枝醋酸乙烯酯的研究

以离子液体1-乙烯基-3-甲基咪唑氯盐([AMIM]Cl)为溶剂,以过硫酸铵为引发剂,制备了木薯淀粉接枝醋酸乙烯酯共聚物.研究了引发剂浓度、醋酸乙烯酯单体与淀粉的配比、反应温度以及反应时间等因素对淀粉接枝醋酸乙烯酯共聚参数的影响,并对淀粉接枝产物进行了红外光谱、XRD、SEM分析.结果表明,在[AMIM]Cl中淀粉接枝...     

共价功能化POSS/PDMS防腐复合涂层的研究

首先采用硅烷偶联剂通过水解缩合反应方法合成氨基功能化倍半硅氧烷(POSS-NH₂),利用其表面氨基通过表面接枝聚合方法在倍半硅氧烷表面接枝磺化聚苯胺以实现其共价功能化,将磺化聚苯胺功能化倍半硅氧烷和聚二甲基硅氧烷通过溶液共混,利用滴涂法在Q235钢材表面制备出疏水防腐涂层。通过核磁共振(NMR)和傅里叶转换红外光谱(FT-IR)对氨基功能化倍半硅氧烷和磺化聚苯胺功能化倍半硅氧烷的结构进行表征分析;利用光电子能谱(XPS)分析磺化聚苯胺功能化倍半硅氧烷的化学组成和元素含量比例;利用扫描电子显微镜(SEM)表征磺化聚苯胺功能化倍半硅氧烷的微观形貌,观察到表面形貌较规整、呈颗粒状、纤维较粗的结构;采用静态接触角测试分析了四种涂层的疏水性,制备出的共价功能化POSS/PDMS防腐复合涂层疏水性最佳,接触角达到115°;采用EIS电化学阻抗谱和Tafel极化曲线测试表征了四种涂层的耐腐蚀性能,结果表明:共价功能化POSS/PDMS防腐复合涂层的腐蚀电位更大,腐蚀电流密度较小,由此表明所制备的材料具有优异的防腐性能。并且发现涂层的接触角越大,防腐性能越好。     

聚二甲基硅氧烷-梯形苯基倍半硅氧烷共聚物的制备

探讨了用羟基硅油(PDMS)和苯基三甲氧基硅烷(PTMS)合成聚二甲基硅氧烷-梯形苯基倍半硅氧烷共聚物的反应条件,通过IR、1H-NMR确定了目标产物的结构.     

Vi-POSS衍生物在液体硅橡胶的应用研究

以乙烯基倍半硅氧烷与七甲基氢三硅氧烷(HMHTS)为原料,按照不同的配比,通过硅氢加成反应制备几种乙烯基倍半硅氧烷衍生物,然后将其与加成型液体硅橡胶进行混合固化,并利用1 H-NMR、XRD、UV-Vis和TG等仪器对固化产物的性能进行表征。结果发现:随着Vi-POSS衍生物结构中七甲基三硅氧基的增多,其与液体硅橡胶的相容性会越来越好,透光率可以达到85%以上;当Vi-POSS衍生物结构中保留2或4个乙烯基时,可以将液体硅橡胶的拉伸强度由3.72MPa提高到6.27MPa;同时还可以显著提高液体硅橡胶的热稳定性。     

聚苯基倍半硅氧烷研究进展

分别介绍了梯型、笼形聚苯基倍半硅氧烷及其共聚物的结构、性质和合成方法,重点综述了苯基倍半硅氧烷共聚物研究进展,并对苯基倍半硅氧烷材料的发展趋势进行了展望。     

Experimental Measurement and Thermodynamic Modeling of the Solubility of Carbon Dioxide in Aqueous Alkanolamine Solutions in the High Gas Loading Region

The solubility of carbon dioxide in aqueous alkanolamine solutions was investigated in the high gas loading region based on experimental measurements and thermodynamic modeling. An experimental phase equilibrium study was performed to evaluate the absorption of carbon dioxide in aqueous solutions of five representative alkanolamines, including monoethanolamine, diethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol and piperazine. The carbon dioxide loadings of these solutions were determined for a wide range of pressures (62.5 kPa to 4150 kPa), temperatures (303.15 K to 343.15 K) and alkanolamine concentrations (2 M to 4 M). The results were found to be largely consistent with those previously reported in the literature. Furthermore, a hybrid Kent–Eisenberg model was developed for the correlation of the experimental data points. This new model incorporated an equation of state/excess Gibbs energy model for determining the solubility of carbon dioxide in the high-pressure–high gas loading region. This approach also used a single correction parameter, which was a function of the alkanolamine concentration. The results of this model were in excellent agreement with our experimental results. Most notably, this model was consistent with other reported values from the literature.     

Applying ANN,ANFIS and LSSVM Models for Estimation of Acid Solvent Solubility in Supercritical CO₂

In the present work, a novel machine learning computational investigation is carried out to accurately predict the solubility of different acids in supercritical carbon dioxide. Four different machine learning algorithms of radial basis function, multi-layer perceptron (MLP), artificial neural networks (ANN), least squares support vector machine (LSSVM) and adaptive neuro-fuzzy inference system (ANFIS) are used to model the solubility of different acids in carbon dioxide based on the temperature, pressure, hydrogen number, carbon number, molecular weight, and the dissociation constant of acid. To evaluate the proposed models, different graphical and statistical analyses, along with novel sensitivity analysis, are carried out. The present study proposes an efficient tool for acid solubility estimation in supercritical carbon dioxide, which can be highly beneficial for engineers and chemists to predict operational conditions in industries.     

Synthesis and characterisation of cerium sulphide over optical fiber and its gas sensing application

In this study, a cladding-modified optical fiber-based gas sensor is proposed for detection of carbon dioxide gas. Cerium disulphide (CeS₂) is synthesised and coated by chemical bath deposition (CBD) route over the region in which cladding is removed. This synthesised cerium disulphide is characterised by x-ray diffraction (XRD), photoluminescence spectrum (PL), ultra violet-visible absorption spectrum, ultra violet -visible reflectance and transmittance spectrum, scanning electron microscope images (SEM) and energy dispersive x-ray spectrum (EDX). The response of the sensor is recorded for different concentrations of test gases (nitrogen dioxide and carbon dioxide) and the sensor's selectivity is compared and analysed. It is observed that cerium disulphide is more sensitive to carbon dioxide compared to nitrogen dioxide.     

二氧化碳在液氧和液氮中的溶解度

求取固体二氧化碳在液氮和液氧等低温液体中的溶解度，对于控制低温流体中二氧化碳的含量至关重要。在理想溶液的基础上，采用了适用于非极性溶质-溶剂的系统的正规溶液关系式和修正的Scatchard-Hildebrand关系式，对二氧化碳在液氮和液氧中的溶解度进行了计算，并与文献中的实验数据进行比较，给出了较为合理的结果，可供工程应用参考。     

Effect of helium in helium headspace carbon dioxide cylinders on packed-column supercritical fluid chromatography

Supercritical fluid chromatography of PAHs was performed with pure carbon dioxide and helium headspace carbon dioxide at various cylinder fill levels. The retention times of the PAHs increased when helium headspace carbon dioxide was used as a carrier fluid relative to pure carbon dioxide. The increased retention times were affected by the level of the liquid phase present in the helium headspace carbon dioxide cylinder. As more liquid phase was removed from the cylinder, the effect of helium on the solvating power of CO(2) was reduced because the relative amount of helium dissolved in the liquid phase decreased. Furthermore, the effect of helium headspace carbon dioxide was investigated with methanol-modified carbon dioxide mobile phases for the analysis of steroids. We observed that the relative solubility of helium in carbon dioxide resulted in longer retention times when compared to pure carbon dioxide as the liquid level of carbon dioxide decreased.     

A comprehensive thermodynamic analysis of a CO<Subscript>2</Subscript>-based heavy metal extraction process

The development of a cost effective CO₂-based hydrometallurgical process was realized through examining the extraction performance of a nearcritical carbon dioxide/CO₂-soluble alkylamine extraction system over a large range of temperatures, pressures, and compositions, as well as through characterizing the phase behavior of the highly CO₂-soluble alkylamines. A most important discovery of this research is that Fluorolink exhibits a higher CO₂ solubility than other fluorinated alkylamines examined in past efforts. Development of these novel polymeric chelating agents is of great utility since these CO₂-philic materials show high solubilities of 15 wt% at 860 psi and 25 °C. In addition to its high thermodynamic affinity for carbon dioxide, Fluorolink was chosen as the model complexing agent because of its ability to target the zinc metal ions of interest and form stable metal complexes. The chelating power of the complexing agent is validated by the large formation constant for the zinc metal complex of 1.0×10¹³ and the quantitative zinc extraction efficiency of 99% attained using a hexane/Fluorolink extractant system. It is because of the materials high CO₂ solubility as well as its chelating power that the complexing agent was capable of extracting zinc in quantitative amounts from aqueous solutions containing high metal loadings of 5,000 ppm while operating at relatively low system pressures of 1,500 psi and below. This analysis validated the extraction mechanism via examination of reagent partitioning behavior, existence of zinc in carbon dioxide, stoichiometry of complexation process, and identification of the anion responsible for charge neutralization.     

Supercritical Fluid Extraction of Actinide Complexes: I. SCE of Adduct of Uranyl Trifluoroacetylacetonate with Pyridine

A number of procedures for determining the solubility of metal complexes in supercritical carbon dioxide (SC-CO₂) were compared. The solubility of adduct of uranyl trifuoroacetylacetonate with pyridine at a pressure of 300 atm and a temperture of 60°C exceeds 100 g l^-1 (26 mg of U per 1 ml of SC-CO₂). Partial degradation of the adduct under these conditions was observed.     

超临界二氧化碳循环发电技术应用

超临界二氧化碳循环可应用于火力发电、核能发电、太阳能热发电等多种发电技术领域,作为新型的动力循环系统替代目前广泛使用的汽轮发电机组或燃气轮机发电机组。在进入商业化应用之前,需要对超临界二氧化碳循环技术在各种应用场景下的优势及其潜在的社会和经济效益进行探讨。通过分析超临界二氧化碳循环的特点和优势,探索其与化石能源、核能、太阳能、生物质能、余热等各种热源相结合的可行性,提出多种发电系统方案,可为今后超临界二氧化碳循环的商业化应用提供参考。随着超临界二氧化碳循环技术不断成熟,设备成本进一步降低,其系统简化、结构紧凑、效率高等优势将更加突显。     

Directs Measurement of High Temperature/High Pressure Solubility of Methane and Carbon Dioxide in Polyamide (PA-11) using a High-Pressure Microbalance

Experiments to determine the solubility of methane and carbon dioxide in PA-11 have been performed in the temperature range 50--90 °C and the pressure ranges 50--150 bar for methane and 20--40 bar for carbon dioxide. In general, the results agree fairly well with previous experiments for similar polymers, as well as showing correct trends in terms of temperature and pressure. The solubility of the gases follows Henrys law-type behavior except for methane at very high pressures. Diffusivities were also measured for the same systems at the same conditions. While the diffusivities are subject to more uncertainty than the solubility measurements, the expected (Arrhenius) trends are observed. Agreement with other experimental data using different methods is also good.Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

Selective extraction of pesticides from lipid-containing matrixes using supercritical binary gas mixtures

When supercritical carbon dioxide is used for extraction of trace compounds from lipid-rich samples, the resulting extract can contain a substantial amount of lipid coextractive which interferes in the subsequent chromatographic analysis. In this case, a cleanup step, which is time-consuming, is required in order to remove or reduce the lipid content in the extract. In this study, we report on a new approach for the extraction of trace compounds which significantly reduces the quantity of lipid coextractives, thereby eliminating the need for a sample cleanup step. An autoclave high-pressure reactor equipped with a mechanical stirring device was used for mixing gases, such as carbon dioxide and nitrogen, to generate the desired fluid mixtures. The composition of the mixtures could be adjusted by two mass flow controllers prior to the autoclave mixing device. The generated carbon dioxide/nitrogen binary mixtures were then employed to facilitate supercritical fluid extraction (SFE) at high pressures and elevated temperatures. The pressurized CO(2)/nitrogen binary fluid mixture demonstrated sufficient solvation power for quantitative recoveries of trace fortified organophosphorus and incurred organochlorine pesticides from poultry fat while significantly reducing lipid solubility in the fluid. This allowed the development of a method that produced an extract with minimal lipid content that could be used directly for gas chromatographic analysis, thereby eliminating the need to clean-up the extract.