2,2-二苯环丙烷酸农药中间体的对映体分离研究

利用Pirkle型(S,S)-Whelk-O1手性固定相对2,2-二苯环丙烷羧酸农药中间体进行了对映体分离研究.考察了在流动相正己烷中,异丙醇的浓度变化对手性分离的影响,初步探讨了其手性识别机理,结果表明,(S,S)-Whelk-01上溶质与固定相之间主要是通过吸引作用发生手性识别.     

Development of Olefin Polymerization Catalysts and Their Commercialization

1TheinternationaltrendonpolyolefincatalystR&DandcurrentsituationinChi na　Therapiddevelopmentofpolyolefinindustryhasacloserelationwiththeprogressinpolyolefintechnology.Catalyst,asacoreofthetechnology ,playsaleadingroleintheevolvementoftheindustry .Withthedevelopmentofcatalyst,polyolefinprocessesaresimplified ,productgradesdiversi fied ,andresinperformanceimproved .Theseprogresseshavewidenedtheapplicationscopeofresinsandbettermetthede mandfromsociety .　Initsdevelopment,threekindsofpolyolefin…     

Palladium（ Ⅱ ） and Platinum（ Ⅱ ） Compounds Derived From Potentially Terdentate Ligands

Transition metal complexes derived from potentially terdentate ligands have attracted great interest in the late years. Among all the examples described so far, those containing palladium（ Ⅱ ） or platinum（ Ⅱ ） and ligands holding three heteroatoms with different donor abilities are particularly relevant. In compounds of this kind, the potential hemilability of one of the terminal σ（M-donor atom） bonds, plays an important role in the view of their applications in homogeneous catalysis. On the other hand, it is well-known that in dimetallic complexes the presence of two different metals in a close vicinity may influence their mutual cooperation in a wide variety of processes. Besides that, some examples of the utility of chiral palladium（ Ⅱ ） as well as platinum（ Ⅱ ） complexes as precursors for organic and/or organometallic synthesis, as chiral recognitors or discriminators, or even in Bio-Medicine have also been reported. However, chiral heterodimetallic compounds holding ferrocenyl units and potentially terdentate ligands are scarce.     

Ethylene Oligomerization and Polymerization: Alternative Iron Catalysts beyond 2,6-Bisiminopyridyl Iron Complexes

1Introduction Polyolefin industry arrives the option to transfer from multiple-site systems of the classical Ziegler-Natta catalysts to more sophisticated single-site catalysts. The late-transition metal compounds were traditionally assumed with poor polymerization properties due to the highly competitive chain-termination step, and produced the short-chain oligomers up to 40 carbon atoms (SHOP catalysts). Recently the polyolefins employing latetransition metal complexes as catalysts became a hot research subject with the pioneering works by Brookhart and Gibson. It is promising for nickel catalysts to use solely ethylene as monomer for highly branched polyethylenes, and the designed nickel catalysts were not useful in industry. It is critical time to investigate the relationship of coordination modes of nickel complexes and its catalytic activities and the properties of resultant polyethylenes.     

Asymmetric Hydrogenation of Ketones-Design of Chiral Catalysts

1Introduction Asymmetric hydrogenation of ketones is one of the most reliable methods for obtaining chiral secondary alcohols. This transformation is not only of academic interest, but also of industrial significance because of its simplicity, environmental friendliness, and economic viability. Chiral RuXY(binap)(1,2-diamine) complexes (BINAP = 2,2'-bis(diphenyl-phosphino)-1, 1'-binaphthyl,X = Y = C1 or X = H, Y = BH4) with[1] or without[2] a strong base catalyze rapid, highly productive asymmetric hydrogenation of various simple ketones in 2-propanol. This reaction, unlike conventional hydrogenation, proceeds selectively at a C = O bond leaving coexisting C = C linkages intact. A range of chiral alcohols are accessible in high enantiomeric purity from aromatic,heteroaromatic, olefinic, and amino ketones by this method[1,2]. However, no universal chiral catalysts exist due to the structural diversity of ketonic substrates. Thus, tert-alkyl ketones and 1-tetralones have remained difficult to be hydrogenated with high reactivity and enantioselectivity. We here report that this problem can be resolved by the use of BINAP/PICA-Ru (PICA = α-picolylamine)[3] or BINAP/1,4-diamine-Ru[4] complexes as catalysts.     

Development and Application of Residue Hydrotreating Packaged Technology

In order to develop China’s heay oil deep processing technology.Fushun Research lnstitute of Petroleum and Petrochemicals (FRIPP),SINOPEC has developed two series of residus hvdrotreating catalysts for vacuum residue and atmospheric residus.which hafe been commercialized in Qilu Petrochemical Co.and Dalian West Pacifie Petrochemical co.(WEPEC)respectively.On the hasis of FRIPP’sresearch,and under the leadership and coordination of SINOPEC headquarters.FRIPP,Luoyang Petrochcmical Enginering Com-pany(LPEC),Maoming Petrochemical Co.and Qilu Petrochemical Co.have cooperate and developed the proprietary S-RHT packaged technology for for sour residus hydrotreating.Using R-SHT technology,the 2Mt/a S-RHT unit has been constructed in maoming pemtochemical Co.and successfully put into two-year stable operation with considerable cconomic,socil and snvironmntal benefits,which built a record among the opertions of the world’s simiklar units.     

萘氧化制苯酐催化剂活性微区模型的探讨

萘氧化制苯酐催化剂活性微区模型的探讨＊段世铎林强杨晓军刘慧英（天津大学化学系，３０００７２，天津）（宁夏大学化学系，７５００２１，宁夏银川）关键词萘制苯酐；催化剂；活性微区萘氧化制取邻苯二甲酸酐是典型的选择性多相催化氧化反应，历史上研究甚早．以往有关...     

生物质焦油催化裂解过程中二次焦油成分

以秸秆热解产生的焦油为原料,在固定床反应器实验台上进行了催化裂解实验,研究了反应温度和催化剂种类对生物质焦油的裂解反应产物———二次焦油成分的影响规律。在高铝砖作为催化剂作用下,随着温度的升高,二次焦油构成有芳香化的趋势,多环芳烃的种类和含量都在增加。反应温度的提高有利于焦油的深度转化,二次焦油产率降低;但是高温下生成的二次焦油芳化程度更高,更容易引起催化剂积炭失活。当反应温度为900℃时,碱性催化剂白云石和石灰岩作用下二次焦油成分相似,以复杂的大分子环烃为主,而且焦油成分种类减少到10种左右;酸性催化剂高铝砖作用下焦油成分仍然很复杂,有将近30种,除了含有大分子环烃外,还含有部分石蜡烃,芳香族种类很多,多以双环、三环以及四环的形式存在。     

环境分析中的手性识别方法展望

环境中广泛存在着众多的天然和人工合成的手性对映体,手性对映体主导着自然界的奇妙和生命的奥秘.在环境分析中需要探索手性对映体污染物的作用和变迁,自然环境中的手性环境能自然开启手性识别和激活手性,而人为介入的手性识别需要高灵敏度和高选择性相结合的分析手段.许多高灵敏度且简便易行的光谱分析方法,借助有机染料、纳米粒子或量子点等手性选择性试剂,或合成设计某些光散射探针试剂可形成高效的选择性手段.筛查手性选择性试剂或手性光散射探针试剂与荧光、散射相结合的手性识别则是一项创新工作.发展不经分离而同时测定手性污染物的新分析方法是一项有意义的探索.     

含氟及手性交联剂的液晶弹性体的合成与性能

合成向列液晶单体:4-((4-烯丙氧基)苯甲酰氧基)苯基-4-氟苯甲酸)酯(M1)和非液晶手性交联剂:双(4-((4-烯丙氧基)苯甲酰氧基)异山梨醇酯)(MC).按不同比例将M1和MC接枝共聚到聚甲基含氢硅氧烷上,得到含氟手性液晶弹性体PI~PVIII.用红外光谱、核磁共振表征单体和聚合物结构,用差示扫描量热仪、热失重仪、偏光显微镜及X射线衍射等手段研究其液晶性能.结果表明,含氟类短而硬的液晶基元更易被手性诱导,出现性能优异的胆甾相.其中,PI为向列型液晶,PII~PVII为出现油丝和Grandjean织构的胆甾型液晶,PVIII没有液晶性.弹性体玻璃化转变温度随着手性交联剂含量的增加先增大后减小,熔点和清亮点均呈下降趋势.所合成的液晶弹性体热稳定性好,质量损失5%时的热失重温度均在300℃以上.