聚合负载三氯化钕配合物的合成及其催化活性——含硫醇和亚砜基团的配合物

合成了含—CH     

电化学聚合漆酚-镨配合物的合成及其表征

通过电化学方法合成的聚合漆物、与氯化镨作用生成聚合漆酚－镨配合物膜。采用原子发射光谱、红外光谱、荧光光谱、差热－热重分析、Ｘ光电子能谱和动态热分析等手段进行表征。探讨其结构与耐热性质。证明了螯合物中存在Ｐｒ＾３＋和ＥＰＵ的配位作用,并引起进一步交联,因而难溶于绝大多数有机溶剂,同时玻璃化转变温度和耐热性能均得提高。     

三水合氯化镨与18C6在乙醇中的配位行为及配合物的合成与表征

采用半微量相平衡方法研究了ＰｒＣｌ_３·３Ｈ_２Ｏ－１８Ｃ６－Ｃ_２Ｈ_５ＯＨ三元体系在２５℃的溶解度，测定了各饱和溶液的折光率。在该体系中有三种比学计量的配合物形成，其化学组成为：２ＰｒＣｌ_３·１８Ｃ６·６Ｈ_２Ｏ·Ｃ_２Ｈ_５ＯＨ、４ＰｒＣｌ_３·３（１８Ｃ６）·１２Ｈ_２Ｏ和ＰｒＣｌ_３·１８Ｃ６·３Ｈ_２Ｏ，依据相平衡结果，合成了三种固态配合物，利用化学分析、ＩＲ、ＴＧ、ＤＴＧ、ＤＳＣ及电导研究了配合物的组成和性质。     

SiO2负载的后过渡金属配合物／三乙基铝催化乙烯聚合研究

将后过渡金属配合物{[2,6-ArN=C(Me)2C5H3N]FeCl2} ( Ar=2,6-iPr2C6H3) Ⅰ负载于SiO2上, 并与三乙基铝(AlEt3)组成催化剂体系并催化乙烯聚合. 考察了Al/Fe比(AlEt3/催化剂摩尔比)、聚合温度对催化剂活性、聚乙烯(PE)分子量、熔融温度以及结晶度的影响. 在Al/Fe比为750、聚合温度为40 ℃时, 催化剂活性达到7.07×105g PE·(mol Fe·h)-1. 实验所得聚合物的分子量为1.05×105～2.33×105 g/mol, 熔融温度高达132 ℃左右,结晶度在44.2%～77.8%之间.     

SBA-15分子筛负载双金属配合物的合成及其催化活性

合成了SBA-15分子筛负载的同双核金属配合物{[M2LCl3]Cl/SBA-15-NH2,M=Co,Cu,Cr,H4L=二(o-亚甲基苯亚甲基三亚乙基四胺}和异双核金属配合物{[CuEuL′](NO3)(H2O)3/SBA-15-NH2,H2L′=N,N′-二(o-羟基-m-甲酰基苯甲基)哌嗪},其结构经UV,1H NMR,IR和元素分析表征。以双核金属配合物为催化剂,过氧化氢为氧化剂,催化二苯甲烷合成二苯甲酮。考察催化剂的种类、反应时间和反应温度对该反应的影响。结果表明,在70℃反应7 h的反应条件下,[Cr2LCl3]Cl/SBA-15-NH2显示了最高的催化活性,二苯甲酮产率达58.1%。     

三水合氯化镨与18C6在乙醇中的配位行为及配合物的合…

采用半微量相平衡方法研究了ＰｒＣｌ３．３Ｈ２Ｏ－１８Ｃ－Ｃ２Ｈ５ＯＨ三元体系在２５℃的溶解度，测定了各饱和溶液的折光率，在该体系中有三种化学计量的配合物形成，其化学组成为：２ＰｒＣｌ３．１８Ｃ６．６Ｈ２Ｏ．Ｃ２Ｈ６ＯＨ，４ＰｒＣｌ３．３（１８Ｃ６）．１２Ｈ２Ｏ和ＰｒＣｌ３．１８Ｃ６．３Ｈ２Ｏ依据相平衡结果，合成了三咱固态配合物，利用化学分析、ＩＲ、ＴＧ、ＤＴＧ、ＤＳ电导研究了配合物的组成和性质。     

Ru-SBA-15的合成、表征及催化活性

在酸性条件下直接合成了Ru-SBA-15．经XRD、N2吸附-脱附、TEM表征其保持了高度有序的六方介孔结构，并在用氧气催化氧化环己烷的过程中表现出了优异的催化性能．     

三铌和三过氧铌钨磷杂多配合物的合成、表征及催化性能

催化活性;三铌和三过氧铌钨磷杂多配合物的合成、表征及催化性能     

β－烷氧羰乙基三氯化锡与水杨醛缩苯胺类Schif碱配合物的合成及表征

由β－烷氧羰乙基三氯化锡与水杨醛缩苯胺类Ｓｃｈｉｆ碱反应，合成了１３种新的有机锡－Ｓｃｈｉｆ碱配合物。经元素分析、ＩＲ、ＮＭＲ和ＴＧ－ＤＳＣ测定，对其结构进行了表征，配合物是通过酚羟基氧原子和锡原子的配键生成的。摩尔电导率测定结果表明，配合物均为非电解质。     

苯磺酰甘氨酸合镨配合物的合成及晶体结构

以苯磺酰甘氨酸(BsglyH)为主配体合成了一维链状配位聚合物[Pr2(Bsgly)6(H2O)4]n·nDMF·1.25nH2O,表征了其晶体结构;采用圆滤纸片和琼脂平板法测定了配合物的抑菌性能.结果表明,配合物属三斜晶系,P1空间群,晶胞参数为:a=1.309 3(4)nm,b=1.644 1(4)nm,c=1.7...     

聚（苯乙烯—丙烯酸）镨配合物中单体链段分布与配合物催化活性的关系

合成并表征了聚(苯乙烯(S)-丙烯酸(A))镨配合物(SAAC·Pr)。红外光谱表明它具有双配位结构:Pr?C—R。计算了共聚物中单体单元的序列分布。苯乙烯和丙烯酸单元长序列分布随其在共聚物中含量的增加而增加。当丙烯酸长序列分布高时,配合物的催化活性低。苯乙烯和丙烯酸的平均链长分别为ns=3,nA=1时,配合物的催化活性最高。     

Synthesis and structures of adamantyl-substituted constrained geometry cyclopentadienyl-phenoxytitanium complexes and their catalytic properties for olefin polymerization

A number of new constrained geometry titanium complexes, [η⁵: η¹-2-C₅Me₄-4-R-6-Ad-C₆H₂O]TiCl₂ [Ad = adamantyl, R = Me (8), ^tBu (9)] and [η⁵: η¹-C₅H₂Ph₂-4-^tBu-6-Ad-C₆H₂O]TiCl₂ (10), were synthesized from reactions of TiCl₄ either directly with corresponding free ligands, 2-C₅Me₄H-4-R-6-Ad-C₆H₂OH [R = Me (5), ^tBu (6)], or with the dilithium salt of the free ligand 2-C₅H₃Ph₂-4-^tBu-6-Ad-C₆H₂OH (7). These new titanium complexes were fully characterized by ¹H and ¹³C NMR spectroscopy and elemental analyses, and the molecular structures of 8 and 9 were determined by single-crystal X-ray crystallography. Upon activation with AlⁱBu₃ and Ph₃CB(C₆F₅)₄ (TIBA/B), these complexes exhibit high catalytic activity for 5-ethylidene-2-norbornene (ENB) polymerization as well as ethylene/1-hexene and ethylene/ENB copolymerization with good tacticity-control ability for the ENB polymerization and high comonomer incorporation ability for the copolymerization reactions. It was found that the bulky adamantyl substituent at the ortho position of the phenoxy group in the ligands of these complexes apparently influences the molecular weight and the microstructure of the resultant polymers.     

聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物的合成与催化性能

γ-氨丙基三乙氧基硅烷与丙烯腈反应，得到γ-(β-氰乙基)胺丙基三乙氧基硅烷。后者用气相法二氧化硅固载，再与氯亚铂酸钾反应，合成了聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物。研究了它对不饱和烃与三乙氧基硅烷的硅氢加成反应的催化特性。     

Synthesis,structure and catalytic polymerization activity of half‐sandwich cyclometallated iridium complexes

A series of mononuclear half‐sandwich cyclometallated iridium complexes with Schiff base ligands were synthesized in good yields. Five air‐stable C,N‐chelate mode complexes were obtained smoothly through metal‐mediated C─H bond activation. Treatments of dimeric metal complexes [Cp*IrCl₂]₂ with ligands L1–L5 afforded the corresponding C,N‐chelate mononuclear half‐sandwich iridium(III) complexes 1 – 5 . These iridium complexes exhibit high catalytic activity for norbornene polymerization. Both steric and electronic effects of the substituted groups have influences on the behaviors of the polymerization process. All complexes were characterized using infrared and NMR spectroscopies and elemental analysis. Molecular structures of complexes 1 , 2 and 5 were further confirmed using single‐crystal X‐ray analysis.     

Hydrolysis of phosphate esters with polymer-supported catalysts containing cyclodextrin pendant group

Polymer-supported catalysts of several kinds, including-cyclodextrin (P-CD),-cyclodextrin-diethylenetriamine (P-CD-DETA), and-cyclodextrin-N-methylhydroxamate (P-CD-NMHA)-containing polymers, as well as their corresponding metal complexes, were synthesized and examined as catalysts for the hydrolysis of phosphate esters. The kinetic measurements were performed in a phosphate buffer (0.05 M, pH 8.2) at a temperature of 25.0±0.1 °C. Each kinetic run was initiated on introducing ester stock solution (0.13 ml) containing diphenylp-nitrophenyl phosphate (DPPNPP) in dioxane (0.010 M). The rate of hydrolysis of DPPNPP was evaluated by measuring the absorbance of liberatedp-nitrophenol at 402 nm. The dissociation constants between DPPNPP and the polymers P-CD, P-CD-DETA and P-CD-NMHA obtained from Eadie-type plots were 16.8, 16.4 and 8.0 (×10^–3 M) and the acceleration factors were 1.5, 2.8 and 8.6 respectively. Hence P-CD-NMHA is the most promising catalyst. The activation parameters, preexponential factor (A) and activation energy using P-CD-NMHA as catalyst, areA=1.2×10⁹ min^–1 andE _a=43 kJ/mol respectively; the latter was about 12 kJ/mol lower than the activation energy of spontaneous hydrolysis. The results indicate that the catalytic power of P-CD-NMHA may reflect the combined behavior of molecular recognition and nucleophilicity.     

A study of polyethylene-gr-2-tert-butyl amino methacrylate-supported TiCl4 catalyst for ethylene polymerization

The use of a polyethylene-based copolymer with dual functional groups (polyethylene-gr-2-tert-butyl amino ethyl methacrylate) as the support for TiCl₄ catalyst in ethylene polymerization was studied. Different methods for treating the support were examined and treatment with BuMgCl was found to be the most effective. With the BuMgCl-modified support, a 12-run Plackett-Burman design was used to screen 11 factors in catalyst preparation. Statistical analysis of the results from this design identified significant factors with the amount of BuMgCl singled out to be the most important one for the four response variables of interest, Mg loading, Ti loading, catalyst activity per gram catalyst, and catalyst activity per gram Ti. © 1996 John Wiley & Sons, Inc.     

二胍基钛配合物的合成及其催化性能

胍上有三个具有给电子能力的氮原子,胍基负离子[(RN)2C(NR2)]-具有多种共振结构,可以多种方式与金属配位;同时它的空间位阻和电荷效应可以很容易通过氮原子上的取代基进行调控。近年来胍基作为辅助配体在主族和过渡金属配合物的合成中的应用引起了人们的广泛关注,而且发现一些胍基金属配合物显示出了不同于茂基金属配合物的独特的反应性质。但是有关胍基钛配合物的合成与反应性能方面的文献报道还很少。本文报道两个胍基钛的配合物的合成,并对它们的催化聚合活性作了初步研究。     

Pr掺杂对Ru/CeO_2催化剂结构和氨合成性能的影响

采用氧化-还原共沉淀法制备了Pr掺杂的Ru/CeO2-PrO2氨合成催化剂,并运用N2物理吸附、X射线粉末衍射、H2程序升温还原、CO化学吸附、N2程序升温脱附、场发射扫描电镜、高分辨透射电镜和X射线光电子能谱等技术对其进行了表征,考察了Pr添加量对催化剂表面结构和性能的影响.结果表明,Pr掺杂对Ru/CeO2催化剂的比表面积和Ru分散度都有所影响.当CeO2中Pr掺杂量为4%时,在425oC,10MPa,10000h–1的反应条件下,氨合成转化频率可达到12.13×10–2s–1,较Ru/CeO2催化剂提高了58%,这主要归结于复合材料电子传导性能的提高.     

Synthesis and characterization of titanium complexes bearing sulfoxide groups and their catalytic behaviors in ethylene homo- and copolymerization

<正>1 Experimental section 1.1 General information All manipulations of air- and/or moisture-sensitive compounds were performed under nitrogen atmosphere using standard Schlenk techniques. 1H NMR and 13 C NMR spectra were recorded on a Varian XL-300 MHz spectrometer with TMS as the internal standard. Mass spectra were obtained using a HP5959 A spectrometer. IR spectra were recorded using a Nicolet AV-360 spectrometer. Elemental analysis was performed by the Analytical Laboratory of Shanghai Institute of Organic Chemistry(CAS). Mn, Mw, and Mw/Mn values of polymers were determined with a Waters Alliance GPC 2000 series at