超临界二氧化碳中的高分子合成

近年来,超临界二氧化碳（sc-CO2）在聚合反应中的应用受到了越来越多的关注。本文主要综述了以sc-CO2为反应介质的自由基聚合、阳离子聚合、过渡金属催化聚合、热致开环聚合、溶胶-凝胶聚合以及氧化耦合聚合的研究概况。一系列研究结果表明sc-CO2是非常有前途的反应溶剂,在高分子合成领域将会有更加广阔的应用前景。     

Synthesis and Characterization of Cobalt-Carbon Core-Shell Microspheres in Supercritical Carbon Dioxide System

The synthesis of cobalt-carbon core-shell microspheres in supercritical carbon dioxide system was investigated. Cobalt-carbon core-shell microspheres with diameter of about 1 μm were prepared at 350 oC for 12 h in a closed vessel containing an appropriate amount of bis(cyclopentadienyl)cobalt powder and dry ice. Characterization by a variety of techniques, including X-ray powder diffraction, X-ray photoelectron spectroscopy, Transmission electron microscope, Fourier transform infrared spectrum and Raman spectroscopy analysis reveals that each cobalt-carbon core-shell microsphere is made up of an amorphous cobalt core with diameter less than 1 μm and an amorphous carbon shell with thickness of about 200 nm. The possible growth mechanism of cobalt-carbon core-shell microspheres is discussed, based on the pyrolysis of bis(cyclopentadienyl)cobalt in supercritical carbon dioxide and the deposition of carbon or carbon clusters with odd electrons on the surface of magnetic cobalt cores due to magnetic attraction. Magnetic measurements show 141.41 emu/g of saturation magnetization of a typical sample, which is lower than the 168 emu/g of the corresponding metal cobalt bulk material. This is attributed to the considerable mass of the carbon shell and amorphous nature of the magnetic core. Control of magnetism in the cobalt-carbon core-shell microspheres was achieved by annealing treatments.     

在超临界CO2聚合反应中应用的表面活性剂的研究

概括了表面活性剂在以超临界CO2 为介质的分散反应和乳化反应中的应用研究进展。重点介绍了几种重要的表面活性剂的结构、机理及应用 ,并指出在应用超临界CO2 技术进行的聚合反应中 ,表面活性剂具有重要的作用及广阔的应用前景。     

用超临界二氧化碳重结晶分离菲蒽混合物

建立了一套以超临界二氧化碳及其改性流体为重结晶溶剂的等压温差超临界流 重结晶实验装置。用色谱保留值法评价了ＳＦＲ分离菲蒽的试验条件。研究了该实验装置影响重结晶的因素，并对同分异构体型菲蒽模型混合物进行了ＳＦＲ分离纯化。     

超临界二氧化碳流体环境中导电聚吡咯复合材料的制备

以聚苯乙烯(PS)和锌盐中和的磺化聚苯乙烯(Zn-SPS)膜为基体, 在超临界二氧化碳(SC-CO₂)环境中用化学氧化法原位制备了聚吡咯(PPy)导电复合材料. 由于SC-CO₂对聚合物基体的强溶胀作用, 吡咯分子高效地扩散到基体内部进行聚合而形成导电通路, 得到比传统的水溶液法更高的电导率. 聚合物基体的性质对复合材料的导电性和形貌产生重要影响. 在相同条件下, Zn-SPS/PPy的电导率比PS/PPy高3~4个数量级, 而它们的体积逾渗阈值分别为2.7%和6.2%, 远远低于理论预测值(16%).     

超临界二氧化碳中聚氨酯对小分子的吸附作用

研究了超临界ＣＯ２中聚氨酯对乙醇、麝香草酚和β－苯乙醇等小分子的吸附作用,观测了超临界ＣＯ２的温度、压力、吸附时间和聚氨酯厚度对小分子吸附量的影响以及小分子在聚氨酯中的释放规律,并探讨了小分子的渗透机理。     

超临界CO_2络合萃取绿茶中Cu、Pb和Cd的研究

本文采用超临界CO2络合萃取法萃取绿茶中的Cu、Pb和Cd。分别考察了不同改性剂和络合剂、萃取压力、萃取温度以及静态和动态萃取时间对三种重金属的萃取率影响。研究结果表明:以磷酸三丁酯(TBP)/HNO3为络合剂,乙醇为改性剂,在20MPa、333K、静态和动态萃取时间分别为30min的最佳条件下,Cu、Pb和Cd的萃取率分别为78.3%、73.2%和69.5%。     

超临界二氧化碳中聚氨酯吸附小分子的影响因素

研究了超临界ＣＯ２中降压时间以及小分子的溶度参数、亲电性和芳香性等因素对聚氨酯吸附小分子的影响,考察了小分子比蒸发速率对小分子在聚氨酯中解吸的影响。结果表明聚氨酯易于吸附亲电性试剂和多数芳香剂族小分子,通常比蒸发速率大的小分子在聚氨酯中解吸也快。     

超临界二氧化碳中丙烯酸与苯乙烯共聚

以超临界二氧化碳为介质, 进行丙烯酸与苯乙烯共聚反应, 合成出具有疏水链段结构的改性丙烯酸聚合物. 研究了压力和投料比对聚合反应的影响. 用红外光谱、紫外光谱和核磁共振谱分析其结构及组成. 采用粘度计测定其水溶液粘度随pH值的变化. 研究结果表明, 该聚合物水溶液具有明显的疏水缔合作用.     

超临界二氧化碳中不同聚合物吸附小分子的比较

研究了超临界二氧化碳中聚氨酯,乙烯醋酸乙烯共聚物和低密度聚乙烯等3种聚合物对几种小分子的吸附作用,观测了吸附小分子后的聚合物的形态变化以及无水乙醇和乙酸乙酯在这3种聚合物中的解吸,实验表明低密度聚乙烯吸附能力较差,不适作吸附的基体材料,而聚氨酯,乙烯醋酸乙烯共聚物吸附小分子能力较强。小分子在聚合物中按时间的自然指数形式递减规律解吸,解吸扩散系数数量级达10-7cm2/s。     

超临界二氧化碳中聚氨酯吸附小分子的影响因素

研究了超临界CO2 中降压时间以及小分子的溶度参数、亲电性和芳香性等因素对聚氨酯吸附小分子的影响,考察了小分子比蒸发速率对小分子在聚氨酯中解吸的影响.结果表明聚氨酯易于吸附亲电性试剂和多数芳香族小分子.通常比蒸发速率大的小分子在聚氨酯中解吸也快     

超临界二氧化碳对不同聚合方法制备的交联聚合物微球的塑化研究

采用分散聚合和无皂乳液聚合的方法,我们制备了粒径不同的交联聚合物微球。通过改变超临界二氧化碳的压力、处理微球的时间以及实验的温度,我们可以实现对这些微球塑化程度的调节。研究发现,随着超临界二氧化碳压力的升高,其对聚合物微球的塑化能力呈现出先增强后降低的趋势。文中我们对这种现象出现的机理也进行了相应的讨论。随着体系温度的升高或者延长处理微球的时间,超临界二氧化碳对两种微球的塑化能力都呈增强趋势。由于乳液聚合得到的聚合物的分子量通常会比分散聚合得到的聚合物的分子量大,因此在相同的条件下超临界二氧化碳对分散聚合法制备的微球塑化能力更强。     

超临界二氧化碳微乳液中的表面活性剂

介绍了在超临界二氧化碳(SC-CO_2)下形成微乳液的原理和概念,并且按照所应用各种表面活性剂的结构特点对其在SC-CO_2下形成微乳液的能力分别进行比较和归纳,为今后筛选和设计在SC-CO_2下形成微乳液的表面活性剂提供了重要信息。     

超临界二氧化碳中马来酸锌催化合成环状碳酸酯

在超临界二氧化碳中, 利用马来酸锌催化二氧化碳与环氧化物反应合成环状碳酸酯. 单独使用马来酸锌作为催化剂时, 对二氧化碳与环氧丙烷反应的催化活性较低, 而在DBU、DMAP、三乙胺、吡啶、咪唑或4-氨基吡啶等有机碱的存在下, 反应活性较高, 产物的收率得到明显提高. 有机碱作用的强弱顺序为DBU>Et3N>咪唑>4-氨基吡啶>DMAP>吡啶. 在压力为8 MPa, 温度110 ℃, 反应时间48 h条件下, 马来酸锌与DBU组成的二元催化系统可以催化二氧化碳与环氧丙烷反应, 得到83.4%产率的碳酸丙烯酯. 该二元系统也能催化其它环氧化物高产率地转化为相应的环状碳酸酯.     

二氧化碳催化还原反应中的光催化剂

总结了CO2光催化还原反应中催化剂的应用，主要涉及TiO2,CdS以及铁氧化物，由于它们自身在反应中存在着一定的缺陷，因而在应用中往往需要对其进行改性，以改变其电子结构和光响应特性，从而提高反应的光催化效率，另外，对催化反应过程所涉及的机理也相应作了介绍。     

Effect of Chain Length on Enzymatic Hydrolysis of p-Nitrophenyl Esters in Supercritical Carbon Dioxide

The effect of chain length on the enzymatic hydrolysis of various p-nitrophenyl esters was investigated. Specifically, the hydrolysis of various esters p-nitrophenyl butyrate (PNPB), p-nitrophenyl caprylate (PNPC), p-nitrophenyl laurate (PNPL), p-nitrophenyl myristate (PNPM) and p-nitrophenyl palmitate (PNPP) was studied in supercritical carbon dioxide (ScCO₂) with lipase (Novozym 435). This indicates that the conversion of nitrophenyl esters decreases with increasing chain length. The effect of various parameters such as amount of water added, temperature, and enzyme loading was studied. The optimum temperature for the hydrolysis of PNPB and PNPC was 50°C but was 55°C for PNPL, PNPM, and PNPP in ScCO₂. The reactions were also conducted in acetonitrile as the solvent, and it was found that the reactions reach equilibrium much faster in ScCO₂ than in acetonitrile. The kinetics of the hydrolysis reactions were modeled using a Ping Pong Bi Bi model.     

Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-1-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr2 and Pb2 extraction in supercritical carbon dioxide.     

Catalytic Formation of Propylene Carbonate from Supercritical Carbon Dioxide/Propylene Oxide Mixture

TheuseofsupercriticalcarbondioxideasasubstitUtesolventforchemicalsynthesisisaveryattractiveareainviewofresourceutiIizationandenvironmentalproblems"'.SinceCO2,whichhasaneasilyaccessibIecriticalpointwithaTcof3l.l'CandaPcof7.3MPa,isnontoxic,nonflammableandinexpensive,itcanreplacehazardousorganicsolventandtherebyprovideavaluablepollutionpreventiontool.Assimilartoothersupercriticalfluids,SC-CO,hasgaslikediffusitivityandliquidIikedensity,andchangingpressureandtemperaturecanvaryitsphysicalpro…     

Theoretical Studies on Critical Properties of Binary System with Supercritical Carbon Dioxide

A new expression of mixing rule is suggested according to the Mayson‘s mixing rule in this paper,which adopts the Redlich-Kwong cubic equation of state and the modifed Chueh-Prausnitz method to calculate the experiment critical points of six binary mixtures CO2 toluene,CO2 cyclohexane,CO2 n-butanal,CO2 i-butanal,CO2 methanol,CO2 ethanol.The coefficients of interaction parameter in the expression of mixing rule were optimized from experimental data.The calculated results of critical temperature and critical pressure meet the experiment data well.The maximum relative errore of temperature and pressure between the calculation results and experiment data are 1.493% and 5.2236% respectively,indicating that the proposed expression of mixing rule is reasonable.This may provide a fundamental method for studying and predicting the properties of supercritical fluids.     

Residual Monomer Reduction in Polymer Latex Products by Extraction with Supercritical Carbon Dioxide

Summary: Extraction of residual monomer from a latex product with supercritical carbon dioxide ((sc)CO₂) in a column was studied. Operating conditions were chosen at 35 °C and 100 bar. For reducing the residual styrene level in a polystyrene latex from 10⁴ ppm to 100 ppm and from 10⁴ ppm to 10 ppm, a countercurrent bubble column with latex as continuous and (sc)CO₂ as dispersed phase is suggested. Monomer partitioning was demonstrated to be a key parameter in the equipment design. Monomer transport was found to be governed by the shuttle effect, caused by Brownian motion of the latex to and from the H₂O/CO₂ interface. The drift-flux approach was followed to determine the column flooding conditions. Small column volumes are obtained. (sc)CO₂ is a promising extraction medium for residual monomer reduction in latex products. Performance towards steam stripping is better as the final residual monomer level becomes lower.