超临界(压缩)二氧化碳介质中的选择氧化

由于超临界二氧化碳（SCCO₂）具有稳定、安全、不燃、清洁无毒、粘度小、扩散快、可压缩的特殊性质,所以使得超临界二氧化碳非常适合作为催化反应的绿色溶剂.除此之外,多种气体在超临界二氧化碳中的溶解度很高,这对于那些受传质阻碍和易引起安全隐患的气相反应来讲,使用SCCO₂作为替代的反应溶剂具有重要的价值。值得指出的是：如果选择超临界二氧化碳作为氧化反应的溶剂,其自身不会发生反应而产生副产物,从而容易得到清洁的产物。本文主要讨论了超临界二氧化碳作为反应介质对醇、烯烃和烷烃等选择氧化反应的影响,通过与传统溶剂比较可以看出超临界二氧化碳作为氧化反应溶剂的优势,对近几年来以分子氧为氧化剂,以超临界二氧化碳为介质的催化选择氧化的反应体系作了综述,并对未来的发展提出了展望。     

Carbon Dioxide Fixation with Dialkyltellurium(IV) Dihydroxides

Aqueous solutions of Me₂Te(OH)₂ and (CH₂)₄Te(OH)₂ readily absorb carbon dioxide giving rise to the formation of the dialkyltelluroxane carbonates (Me₂TeOTeMe₂CO₃)_n ( 1 ) and HO(CH₂)₄TeOTe(CH₂)₄CO₃Te(CH₂)₄OH·2H₂O ( 2 ·2H₂O), which were characterised by ¹³C MAS and ¹²⁵Te MAS NMR spectroscopy as well as X‐ray crystallography. The spatial arrangement of the tellurium atoms is defined by C₂O₂ donor sets in the primary coordination sphere and one or two secondary Te···O contacts, which involve coordination of the carbonate moieties. In turn, the different Te–O coordination modes render a lack of symmetry to the carbonate moieties, which show significantly different C–O bond lengths, an important feature when contemplating the C–O bond activation in carbonates. The structural and spectroscopic parameters of 1 and 2 are discussed in comparison with other heavy p‐block element carbonates. In solution, electrolytic dissociation of 1 and 2 takes place.     

Deconstructive Carboxylation of Activated Alkenes with Carbon Dioxide

Carboxylation with carbon dioxide (CO₂) represents one notable methodology to produce carboxylic acids. In contrast to carbon–heteroatom bonds, carbon–carbon bond cleavage for carboxylation with CO₂ is far more challenging due to their inherent and less favorable orbital directionality for interacting with transition metals. Here we report a photocatalytic protocol for the deconstructive carboxylation of alkenes with CO₂ to generate carboxylic acids in the absence of transition metals. It is emphasized that our protocol provides carboxylic acids with obviously unchanged carbon numbers when terminal alkenes were used. To show the power of this strategy, a variety of pharmaceutically relevant applications including the modular synthesis of propionate nonsteroidal anti-inflammatory drugs and the late-stage carboxylation of bioactive molecule derivatives are demonstrated.     

超临界二氧化碳体系中正八面体氧化钴颗粒的生长及其表征

研究了正八面体氧化钴颗粒在超临界二氧化碳体系中的合成过程。在密闭的不锈钢高压反应釜中,1.0 g乙酸钴和12.0 g干冰在450 ℃下,反应12 h后合成粒径大约10 μm的正八面体氧化钴颗粒。通过XRD、 XPS、TEM、 SEM以及拉曼光谱的分析,氧化钴颗粒是由八个{111}面包裹着的正八面体单晶组成。条件实验显示,超临界二氧化碳体系是正八面体氧化钴颗粒合成的充分条件。其生长机理可能是：乙酸钴在超临界二氧化碳体系中的热分解;氧化钴的结晶和定向缓慢生长。在性能方面,初步研究了正八面体氧化钴颗粒在作为锂离子电池电极材料的应用。     

Effect of Chlorine and Nitrosyl Chloride on Nitrogen(II) Oxide Oxidation into Nitrogen(IV) Oxide

The effect of chlorine and nitrosyl chloride impurities on the regeneration of nitrogen(IV) oxide—oxidizing agent in oxychlorination of hydrocarbons—was studied at two temperatures. An assumption is made that the process occurs by radical-chain mechanism and involves chlorine oxides.     

The Oxidation of Cyclohexene with Polymer Supported Co(II) in Supercritical Carbon Dioxide

It is known that a small change in the pressure near critical point of a fluid causes a significant change in density-dependent properties, such as the solubility parameter, viscosity, and dielectric constant1. Recently, there has been a growing interest in using supercritical fluids (SCFs) as reaction media2, 3. Homogeneous catalysts are capable of high specific activity and selectivity. But their removal from the reaction mixtures is difficult4. The application of reusable polymer-bond…     

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…     

用超临界CO2制备疏水改性聚丙烯酸

用超临界CO2制备疏水改性聚丙烯酸;丙烯酸十八酯;超临界二氧化碳;疏水缔合     

Swelling of Polyheteroarylenes in Supercritical Carbon Dioxide

Two series of polyheteroarylenes have been investigated with regard to their physical properties before and after swelling with supercritical carbon dioxide. The study of the dependence of glass transition temperature and free volume of polymers on their conformational rigidity showed that the process of swelling in supercritical carbon dioxide is influenced by the voluminous side groups and by the high boiling solvent N-methylpyrolidinone used for the preparation of the polymers which facilitates the formation of crosslinks or complexes with the macromolecular chains.     

Diiodination of Alkynes in supercritical Carbon dioxide

A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.     

超临界二氧化碳中含氟聚合物的合成

超临界二氧化碳是廉价、低毒、不易燃、易回收、环境友好的惰性聚合介质,是传统有机溶剂的替代品。尤其是有望成为含氟单体的聚合溶剂,以替代目前使用的氟氯烃。本文详细地介绍了近年来以超临界二氧化碳为介质的氟烷基丙烯酸酯类单体和氟烯烃类单体的聚合反应研究,其中涉及氟烷基丙烯酸酯类单体的均聚和共聚,可熔融加工的四氟乙烯聚合物,离子交换树脂,偏氟乙烯的均聚和共聚合等。研究表明在超临界二氧化碳中的含氟单体的聚合反应有其它溶剂体系无法比拟的优点。     

超临界CO2在高分子合成与制备中的应用

介绍超临界二氧化碳流体作为介质在高分子合成与制备中的研究进展。文中表明，可在超临界二氧化碳中实施氟代单体的自由基溶液聚合、甲基丙烯酸甲酯的分散聚合、丙烯酸的沉淀聚合、丙烯酰胺的反相乳液聚合以及异丁基乙烯基醚的阳离子聚合等多种聚合反应，可用超临界二氧化碳溶胀聚合法制备梯度共混物。此外，超临界二氧化碳还可用于聚合物分级和聚合物微孔、微纤与微球材料的制备等，显示出超临界二氧化碳是一种对环境无污染且价廉的     

Visible-Light-Promoted Catalyst-Free Oxyarylation and Hydroarylation of Alkenes with Carbon Dioxide Radical Anion

Visible-light-mediated oxyarylation and hydroarylation of alkenes with aryl halides using formate salts as the reductant and hydrogen source under ambient conditions were developed. These protocols represent rare catalyst-free examples of the realization of such transformations. Using styrenes as substrates, oxyarylation could occur smoothly. Whereas, hydroarylation proceeds employing electron deficient alkenes. Moreover, dehalogenation proceeds successfully in the absence of alkenes. We expected that this method could provide a valuable strategy for the functionalization of aryl halides.     

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.     

钴(Ⅱ)配合物与卟啉在超临界二氧化碳中的反应动力学研究

用紫外-可见光谱研究了1,1,1,5,5,5-六氟-2,4-戊二酮-钴(Ⅱ)二水[Co(hfac)2(H2O)2]与5,10,15,20-四(五氟苯基)卟啉(H2tpfpp)在超临界二氧化碳中反应生成钴卟啉[Co(tpfpp)]的反应动力学.在钴(II)配合物大大过量时,此反应对卟啉为一级,且其表观一级速率常数随钴(Ⅱ)配合物的浓度增加先增加、而后趋于稳定.根据实验事实,讨论了此反应的机理,得到了相应的热力学和动力学参数.     

Extraction of Uranium from Aqueous Solutions by Using Ionic Liquid and Supercritical Carbon Dioxide in Conjunction

Super powers! Uranium(VI) ions can be extracted from aqueous solutions into supercritical CO₂ (sc‐CO₂) via an ionic liquid phase that contained tri‐n‐butyl phosphate (TBP) as a complexing agent (see figure). This process has potential applications in the nuclear industry for removing actinides from nuclear waste.

     

高聚物在超临界二氧化碳介质中的溶胀行为

研究了LDPE、PP、PA6、EVA、PS、PU六种聚合物在超临界CO2 中的溶胀情况 ,观测了溶胀温度、溶胀压力、溶胀时间和降压时间对聚合物溶胀前后重量变化的影响以及溶胀后聚合物中CO2 的解吸曲线。     

超临界二氧化碳中布洛芬响应因子的研究

应用高压紫外检测器在线测定了布洛芬在超临界二氧化碳中的响应因子。 考察了温度、压力和CO2密度等参数对它的影响。在温度298-333K、压力9-17MPa范围内超临界CO2中布洛芬的响应因子随CO2密度的增加而线性递减。建立了布洛芬在超临界CO2中响应因子的经验计算式(回归系数r=0．97)，其理论计算结果与实验数据吻合良好，最大误差≤10％。     

聚乙二醇在超临界二氧化碳介质中的结晶行为

利用DSC和偏光显微镜研究了聚乙二醇在超临界CO2 中的结晶情况 ,超临界条件下得到的晶粒小而均匀 ,DSC测试还表明超临界CO2 可提高聚乙二醇的熔眯和溶解焓。