固体碱KF/Al_2O_3在过渡金属催化的偶联反应中应用研究进展

自Clark和Ando的等发现KF/Al2O3的特殊性能以来,KF/Al2O3在诸多类型的有机反应中得到应用,并取得了满意的结果。近年来,化学科研工作者不断地对其进行深入的研究,使其在更多有机合成领域得到应用。综述了近年来固体碱KF/Al2O3在过渡金属催化的偶联反应中应用的研究进展。     

纳米催化剂KF/Al_2O_3制备条件的正交设计与优化

采用正交设计法优化了浸渍法制备固体超强碱KF/A l2O3催化剂工艺参数。以丙烯腈和丙二酸二乙酯的M ichael加成反应收率为考察指标,对催化剂制备工艺进行优化,并采用SPSS统计软件包对制备工艺参数进行多元回归统计,并根据回归拟合的多项式数学模型,讨论了浸渍法制备的较佳工艺。     

KF／Al2O3在有机合成中的应用

KF/Al_2O_3在烷基化、羟醛缩合、Michael 加成、Knoevenagel 缩合等有机反应中的应用:讨论了其催化作用的机理。     

CoMo/Al_2O_3-SiO_2催化剂原位红外光谱研究

采用原位红外光谱技术,以CO作为探针分子研究了加氢脱硫CoMo/Al2O3-SiO2催化剂的活性吸附位的变化规律。原位硫化温度范围为300~550℃,获得了CoMo/Al2O3-SiO2催化剂的MoS(2110cm2-1)和CoMoS(2070cm-1)活性相在增加硫化温度过程中的转变规律。在CoMo/Al2O3-SiO2催化剂中,当载体中SiO2含量逐渐增加时,能够显著改变催化剂活性相的相对强度变化,表明载体中加入适量的SiO2能够显著改变加氢脱硫CoMo/Al2O3-SiO2催化剂的载体与活性金属(Co和Mo)的相互作用,从而提高金属在加氢催化剂载体上的分散性能,产生更多活性吸附位。     

固体碱KF/Al2O3合成烯丙基缩水甘油醚

固体碱KF/Al2O3具有很好的催化活性,在有机合成反应中具有广泛的应用。主要研究用固体碱KF/Al2O3催化合成烯丙基缩水甘油醚,探索出最佳工艺条件:反应温度为50℃,反应时间为3 h,物料配比n(烯丙醇)∶n(环氧氯丙烷)∶n(固体碱KF/Al2O3)∶n(相转移催化剂)=1∶3∶1.5∶0.015,收率可达到93.1%,产品纯度达到99.2%。     

Fe/Mn/Al_2O_3催化H_2O_2降解偶氮染料废水的研究

以活性氧化铝为载体,制备了Fe/Mn/Al2O3负载型催化剂,用于催化H2O2氧化降解偶氮染料活性黑5,探讨了pH、H2O2投加量、染料初始浓度、催化剂投加量等对染料脱色率的影响。结果表明,活性黑5的脱色率随催化剂投加量、H2O2投加量的增加而升高;而随活性黑5初始浓度的增加而降低。当H2O2投加量的增加达到200 mg/L后,H2O2投加量的增加对活性黑5脱色效果的影响不显著。Fe/Mn/Al2O3/H2O2体系下,活性黑5在pH为2⁹之间均有一定的脱色效果,活性黑5的脱色率随初始pH的增加而先增加后减少,其中在初始pH为3时脱色效果最佳。     

Al_2O_3/金属多相材料研究进展

阐述了Al2 O3 /金属多相材料的研究进展状况 ,对目前已经研究的体系、制备工艺、显微结构与性能以及目前存在的问题和发展趋势等进行了概括 ,重点对其功能化进行了比较详细的阐述。此外 ,也介绍了我们在功能化方面所得到的一些有用的结果。     

K_2O-MgO/Al_2O_3的制备及其在丙酮缩合中的应用

以Al_2O_3和MgO粉体为原料,KOH为改性剂,采用机混法制备了酸碱双功能催化剂,并以丙酮气相合成异佛尔酮为研究对象,优化了催化剂制备条件,并通过透射电子显微镜(SEM)和程序升温脱附法(TPD)对催化剂结构和性质进行了分析。结果表明,n(Mg)∶n(Al)催化剂适宜的制备条件是:压片焙烧温度为500℃,KOH浸渍时间为6h,KOH改性后焙烧温度为300℃,丙酮转化率和异佛尔酮选择性分别为9.6%和68.4%。由表征结果可知,压片焙烧温度过高易使催化剂表面发生烧结,产生较强的酸中心和较小的酸碱量,导致催化剂活性下降。     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

Fe_2O_3/Al_2O_3催化剂制备及催化降解酸性染料废水

以γ-Al2O3>为载体,采用浸渍-焙烧法制备了Fe2O3/Al2O3催化剂.并将其用于催化降解模拟酸性大红-3R染料废水.对于质量浓度为1 000 mg/L的高浓度酸性大红-3R染料废水,最佳的处理工艺条件为:温度60℃、pH=3.0、H2O2投加质量浓度9.4g/L、催化剂投加质量浓度1.5 g/L.在此工艺条件下酸性大红染料废水的降解率为99%,CODCr的去除率>83%.而对于质量浓度≤100 mg/L的酸性大红-3R染料废水在此条件下的降解速率接近100%.且催化剂连续使用6次后仍有较高的催化活性.     

Applications of Michael addition chemistry in coatings technology

Since the first filings of patent applications on the use of the Michael addition as crosslinking reaction for coatings around 1984, a lot of research work has been carried out on its application in practical systems. Initial work on the development of coatings for aircraft, car refinishing and timber showed that, especially with urethane acrylate/malonate polyester combinations, the expected high level of durability could be achieved. Further developments in the field of high solids coatings revealed inhibition problems however. They were caused by the interaction of the strong bases, used as the catalysts for the Michael reaction, with acidic ingredients from the substrate and with carbon dioxide from the atmosphere. In principle the problem can be solved by using higher doses of catalyst, but the potlife is too short for general use then. Temporary blocking of the catalysts with an alcohol or with carboxylic acids was investigated as a way to achieve an acceptable potlife. The use of catalysts blocked with carboxylic acids, deblockable with heat or UV light, is a good solution for industrial coatings. Blocking with an alcohol helps to solve the problem of inhibition by carbon dioxide but not the problem of inhibition by the acidic sites in the substrate.     

用KF/Al2O3催化合成肉桂酸的研究

采用KF/Al2O3催化剂催化合成肉桂酸.用新催化剂催化反应可以降低反应温度,缩短反应时间,提高肉桂酸的产率.探索出了最佳反应条件当反应温度控制在160℃,苯甲醛和乙酸酐的摩尔比1∶3,用6.0 g KF/Al2O3催化反应1.0 h,得到肉桂酸的产率为85.4%.     

Michael加成反应及其在天然产物全合成中的应用

综述了各种类型Michael加成反应及其机理,以及Michael加成反应在天然产物和具有生物活性的复杂化合物合成中的应用。     

KF/Al_2O_3催化下亚胡椒基丙醛的合成

KF Al2O3作催化剂,催化洋茉莉醛和丙醛进行Claisen-Schmidt缩合反应合成了亚胡椒基丙醛。通过正交实验确定了适宜的工艺条件,洋茉莉醛∶丙醛为0 3∶0 42(摩尔比),14g催化剂,丙醛滴加时间2h,反应温度60℃～70℃,反应时间2h。平均摩尔收率80 2%。     

Enhanced fluorescence and thermal sensitivity of polyethylenimine modified by Michael addition

Polyethylenimine (PEI) with enhanced fluorescence and thermal sensitivity was achieved by Michael addition of divinylsulfone (DVS) and N-isopropylacrylamide (NIPAm) respectively. The fluorescence enhancement is quantitatively studied by tailoring the amount of DVS, the medium pH, the substituting acrylates, the substrate polymers with different type amine groups, and the substrate molecular weights. The results suggested that different amine groups affected the performance of fluorescence with quantum yields varied from 0.340 for primary amine (NH₂-) to 0.090 for tertiary amine (N(-C)₃), and further to 0.049 for secondary amine (-NH-). It was also found that the fluorescence enhancement was attributed to the specific molecular structure of DVS-substituted product. The fluorescence moiety is believed to involve a proton-transfer process and have O₂-dependent and pH-sensitive fluorescence properties. From the current study, it can be expected that the accurate prediction of the O₂-dependent fluorescence would be dependent on molecular orbital calculation of the small amine molecules (oxidized with O₂) and their DVS-substituted products.     

Ti3SiC2/Al2O3复合材料的制备与性能研究

以TiC／TiO2/Si／Al／Ti等为主要原料，采用热压法原位合成Ti2SiC2／Al2O3复合材料，分别探讨了Al掺入量和工艺制度对Ti3SiC2/Al2O3复合材料物相、显微结构以及性能的影响。结果表明：原位合成制备的Ti3SiC2/Al2O3复合材料与传统方法合成制备的纯Ti3SiC2材料相比，材料的硬度和致密度均有很大的提高。     

Al2O3/Y-TZP复相陶瓷的力学性能及耐磨性

通过常压烧结制备了Al2O3/Y-TZP复相陶瓷,研究了Al2O3含量对材料力学性能及耐磨性的影响。体积分数为35%Al2O3的Al2O3/Y-TZP复相陶瓷具有相对高的韧性(12.5MPa·m1/2)和较低的磨损率(9.2×10-6mm3/(m·N))。     

Increased stability in self‐healing polymer networks based on reversible Michael addition reactions

A reversible thiol‐ene click reaction is utilized to design novel self‐healing polymers. These materials are based on a new methacrylate monomer featuring a benzylcyanoacetamide derivative, which is copolymerized with butyl methacrylate. Afterwards, the crosslinking is performed by the addition of a dithiol and a tetrathiol, respectively. Self‐healing behavior is obtained by heating the crosslinked polymers to 100 °C (150 °C) for several hours and is monitored by scratch healing experiments utilizing an optical microscope. The thermal properties are studied in detail by differential scanning calorimetry as well as thermogravimetric analysis. Moreover, depth‐sensing indentation measurements are performed to determine the mechanical properties. The healing process is based on the reversible cleavage/closing of the bonds (i.e., thiol‐ene reaction), which could be demonstrated by Raman spectroscopy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44805.     

Synthesis and characterization of hyperbranched poly(ester-amine) by Michael addition polymerization

A series of tertiary amine-based hyperbranched poly(amine-ester)s have been synthesized by Michael addition polymerization of trifunctional monomer, TMEA and difunctional monomer, diacylates in chloroform, and the resultant polymers were subsequently treated with mercaptoethenol or 1-dodecanethiol for improving stability in storage. The caption efficiency of mercaptoethanol is much better than that of 1-dodecanthiol. Kinetic study reveals that the thiol group is consumed faster than the acrylate group when the polymerization with feed molar ratio of diacrylate/TMEA = 2/1 was carried out. At initial polymerization, monomer conversion increases fast, but the molecular weights increase slowly and sharp increase of the molecular weight occurs at the final polymerization. The hyperbranched polymers were well characterized by ¹H NMR spectra and TD-SEC, and DBs of the polymers obtained are between 0.6 and 0.82, as well as the molar ratios of diacrylate/TMEA in the hyperbranched polymers are between 1.60 and 1.82. The fluorescence efficiency and quantum yields of HypET20, HypHT24 and HypDT24 has the following sequence: HypET20 > HypHT24 > HypDT24.