Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Synthesis and application as polymer electrolyte of hyperbranched polyether made by cationic ring‐opening polymerization of 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxymethyl}‐3′‐methyl‐oxetane

A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF₃·Et₂O as initiator through cationic ring‐opening polymerization. The evidence from ¹H and ¹³C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10^?5 S/cm at room temperature and 6.3 × 10^?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006     

STRONG LAW OF LARGE NUMBERS AND ASYMPTOTIC EQUIPARTITION PROPERTY FOR NONSYMMETRIC MARKOV CHAIN FIELDS ON CAYLEY TREES

Some strong laws of large numbers for the frequcncies of occurrence of states and ordered couples of states for nonsymmetric Markov chain fields(NSMC)on Cayley trees are studied.In the proof,a new technique for the study of strong liinit theorems of Markov chains is extended to the case of Markov chain fields.The asymptotic equiparti- tion properties with almost everywhere(a.e.)convergence for NSMC on Cayley trees are obtained.     

Theoretical analysis on waveform structures of pulse propagating in shallow water with an ideal thermocline

I.IntroductionDuetospatia1andtemporalvariabilityoftheocean-acousticenvironment,especially,theeffectsofboundaryaswel1asmediumonpropagationofacousticwavesinshal1owwater,theacousticpropagationisextrcmelycomp1icatcd.Multipathtransmissionisthebasiccharacteris-hcsofunderwatersoundchannels.Undctcrminedmultipathstructurescangreatlylimittheperformanceofunderwateracousticdetcction.However,ifthemultipathcharacteristicsofacousticpropagationinunderwatcrsoundchanne1sareknown,spaee-timeresolutionandpro-cess…     

The measurements of correlation times of molecules adsorbed on silica gel,alumina and charcoal using NOESY and MAS NMR

The correlation times (τ_c) and cross relaxation rates of toluene, dimethylformamide, tetrahydrofuran, water-acetone and water-dioxane adsorbed on silica gel, alumina and charcoal were obtained by measurements of the integrated intensities of cross and diagonal peaks in their NOESY spectra. The (τ_c) of the above mentioned systems is in the range of 10^?6?10^?9 s, much longer than that in the liquid (10^?12?10^?14 s). It was found that intramolecular rotation of toluene adsorbed on charcoal is slower than that on SiO₂, Al₂O₃ and the inversion of α and β protons in tetrahydrofuran is very fast (τ_c = 1.76×10^?9 s). The cross relaxation plays an important role in the relaxation of molecules adsorbed on solid surfaces with low electron densities.     

活性炭酸处理对CuO／C催化剂上NO还原反应的影响

４种国产活性炭被用于ＮＯ还原反应，其中，山楂核炭和山桃核炭具有较高的ＮＯ还原转化率。实验发现，表面含氧基团－ＣＯＯ－对活性炭自身的还原性和对ＮＯ的还原活性有很重要的影响。对表面富－ＣＯＯ－基团的活性炭，稀盐酸处理使表面－ＣＯＯ－显著分解。     

负载型双金属簇催化剂的多相一氧化碳加氢反应性能

负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶，李晔（内蒙古工业大学化学工程系，呼和浩特０１００６２）殷元骐，金道森（中国科学院兰州化学物理研究所，兰州７３００００）关键词一氧化碳加氢，多相催化，双金属簇催化剂，钾效应。１．引言异核金属羰基簇作...     

纳秒激光闪光光解装置功能扩展──有机非线性材料二阶非线性系数测定

纳秒级激光闪光光解装置可用于有机光化学、光物理过程，瞬态发光和吸收的动力学过程的研究，在不改变原装置整体布局和结构的基础上，建立了有机非线性光学材料的二阶非线性系数测定方法，并为国家８６３专家委员会承担过仲裁测定。