Pd/Ce_(1-x)Mn_xO_2催化苯酚氧化羰基化合成碳酸二苯酯

分别采用机械混合法、溶胶-凝胶法和沉淀法制备了用于非均相催化苯酚氧化羰基化一步合成碳酸二苯酯(DPC)的催化剂载体(Ce_(1-x)Mn_xO_2);通过沉淀法负载活性组分 Pd 制备了0.5%Pd/Ce_(1-x)Mn_xO_2(Pd 质量分数0.5%)催化剂。采用 X 射线衍射、扫描电子显微镜和 BET 等方法对 Ce_(1-x)Mn_xO_2载体进行了表征,考察了 Ce_(1-x)Mn_xO_2载体的制备方法和焙烧温度、载体的n(Mn):n(Ce+Mn)对0.5%Pd/Ce_(1-x)Mn_xO_2催化剂活性的影响。实验结果表明,采用溶胶-凝胶法、n(Mn):n(Ce+Mn)=0.50、600℃下焙烧6 h 制备的 Ce_(1-x)Mn_xO_2载体所制得的0.5%Pd/Ce_(1-x)Mn_xO_2催化剂的活性最高,反应在65℃、5MPa 下进行3 h,DPC 收率可达9.3%。     

Synthesis and properties of poly(phenylene sulfide)s containing carbonyl and sulfonyl groups

With a view to study and compare the properties of poly(phenyienc sulfide)s containing carbonyl and sulfonyl backbone units, 1,4-bis(phenylthio)-benzene, and bis(4-phenylthio)diphenyl sulfone, were prepared and subjected to Fricdel-Crafts type polycondensation with various aromatic diacid chlorides. The resulting polymers had inherent viscosities in the range 0.101—0.141 dl/g. These polymers were not soluble in common organic solvents and exhibited good thermal stabilities.     

Synthesis of tellurium containing syndiotactic polymethyl methacrylate using diphenyl ditelluride as a novel initiator

The synthesis of syndiotactic polymethyl methacrylate containing tellurium by using diphenyl ditelluride in the dioxan at (60 ± 0.1)°C for 2 h has been carried out. The presence of tellurium in the polymer has been confirmed qualitatively as well as by induced coupled plasma mass spectroscopy (ICP‐MS). The electron spin resonance spectrum shows the presence of T?Ph, and value of gyromagnetic constant g has been calculated as 2.2203. The T_g of the polymer, measured by DSC, is 105°C. The syndiotactic nature has been confirmed by FTIR and NMR spectroscopy and DSC. The system follows ideal kinetics with activation energy 66 kJ mol^?1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1017–1022, 2006     

膦氮双齿配体/钴催化的相转移氯苄羰化合成苯乙酸

考察了二苯基氨基吡啶膦／Ｃｏ２（ＣＯ）８配合物对相转移催化氯苄羰化合成苯乙酸的催化活性，找出了较佳的反应工艺条件。在反应温度７０℃，ＣＯ压力０．１ＭＰａ，以苄基三甲基氯化铵为相转移剂（ＰＴＣ）时，氯苄的转化率可达９７％，苯乙酸的选择性达９４％。通过动力学研究，测得反应表观活化能为１８．６ｋＪ／ｍｏｌ     

Occurrence of polybrominated diphenyl ethers and polychlorinated biphenyls in shark liver oil supplements

Results are reported of a pilot survey of concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in shark liver oil supplements. Eleven brands of dietary supplements were analysed using an isotope dilution GC/MS method. Total concentrations of 10 PBDE congeners (BDE-28, -47, -49, -66, -99, -100, -153, -154, -155 and -183) ranged from 0.1 to 53 ng g^-1 oil weight and total concentrations of six PCB congeners (CB-28/31, -52, -118, -153 and -180) in the samples ranged from 16 to 340 ng g^-1 oil weight (undetected values are not included). Two brands of Japanese deep-sea shark liver oil contained the highest levels of PBDEs (49-53 ng g^-1 oil weight) and PCBs (290-340 ng g^-1 oil weight). These results indicate that PBDEs may have entered Japanese deep-sea waters.     

固体酸催化合成二苯甲烷二氨基甲酸酯

综述了固体酸催化合成二苯甲烷二异氰酸酯的中间体二苯甲烷二氨基甲酸酯的研究现状。简要介绍了本课题组的研究结果,结合自己的研究内容,提出了杂多化合物催化剂的改进方向。     

苯并噁嗪二苯醚树脂的固化行为研究EI

研究了苯并 口恶嗪二苯醚树脂固化时的体积收缩率、固化温度和固化焓变等。结果表明 ,这类新型树脂在室温下 ,固化收缩小于环氧树脂。在高温下 ,固化收缩率与环氧树脂相当。     

封端基对全对位聚芳醚酮酮热性能的影响

以二苯醚（DPE），对苯二甲酰氯（TPC）为单体，无水AlCl3/二氯乙烷（DCE）／N－甲基吡咯烷酮（NMP）为催化剂溶剂体系，在Friedel-Grafts亲电聚合条件下合成了一系列端基不同的聚芳醚酮酮（PEKKs)，同时测定了聚合物的对数比浓粘度，进行了耐溶剂性试验,X射线衍射，IR，DSC，TG等表征分析，较系统地考察了不同封端对全对位聚芳醚酮酮热性能的影响。研究结果表明，随着封端基碳数的增加，Tm,Tc,Tg,Td呈下降趋势，但仍然保持良好的耐热性。     

ZnCl_2催化草酸二苯酯脱羰基合成碳酸二苯酯

研究了ZnCl2催化剂催化草酸二苯酯脱羰基合成碳酸二苯酯反应,考察了反应温度、反应时间、草酸二苯酯和催化剂摩尔配比对碳酸二苯酯选择性、碳酸二苯酯收率和草酸二苯酯转化率的影响,确定了最佳的反应条件是反应温度280℃,反应时间3h,草酸二苯酯和催化剂摩尔配比是100∶0 5。运用MXXC、Benson等基团贡献法,对草酸二苯酯脱羰基反应的平衡常数进行了估算,得到KP=1 3×109。确定了草酸二苯酯脱羰基反应的副反应,发现水在草酸二苯酯脱羰基合成碳酸二苯酯体系的副反应中起到了关键性作用。草酸二苯酯在酸催化剂作用下易发生水解反应,水的存在有利于副产物苯酚和水杨酸苯酯的生成。因此,限制反应体系中水的含量有助于碳酸二苯酯的生成。     

Pd/CuO-Ce0.5Mn0.5O2催化剂氧化羰基化合成碳酸二苯酯

采采用2种CuO引入方法制备了CuO-Ce0.5Mn0.5O2载体,再通过沉淀法负载活性组分Pd得到了0.5%Pd/CuO-Ce0.5Mn0.5O2催化剂,以XRD, SEM, BET等手段对催化剂进行了表征. 将该催化剂用于苯酚氧化羰基化合成碳酸二苯酯的反应,考察了引入CuO对催化剂催化活性的影响. 结果表明,采用溶胶-凝胶法添加不同含量的CuO时,载体的孔结构及活性组分在载体表面的分散都得到了不同程度的改善;在CuO添加量为9%(w)的条件下,反应在温度75℃、压力5 MPa下进行12 h,碳酸二苯酯收率可达17.06%.