不同配体稀土催化剂下二氧化碳/环氧化物共聚物的合成与性能研究

本论文选用不同取代基及取代位置的芳香梭酸类和磺酸类稀土配合物、烷基锌、甘油组成的三元催化体系，用于二氧化碳与环氧化合物的二元和三元共聚合反应。探讨了稀土三元催化剂的不同配体对聚合产物的收率和聚合物结构的影响，进一步明晰了稀土催化体系与聚合物结构和性能之间的关系。本论文的创新点和主要结果如下：1．在三元催化体系中引入稀土络合物，提高了活性中心（Zn-O-）中的锌内层电子结合能Zn（2p_(3/2)），结合催化剂的紫外可见光谱的红移效应，证明三元 催化体系中已形成了缺电性（氧化态）较强的活性中心，从而提高了CO_2和环 氧化物单体的配位插入反应速率，使聚合产物的收率比二元催化体系提高30％以上；2．芳香环上取代基的性质和取代位置是影响聚合产物收率和分子量分布的重要因素。在芳环上引入推电子基团的甲基或轻基，催化活性表现出相同的变化规律：对位＜邻位＜间位；若引入硝基类吸电子基团，催化活性的规律如下：邻位＜间位＜对位。邻位和对位取代的稀土三元催化体系更容易导致链转移反应的发生，导致聚合物的分子量分布变宽；3．二氧化碳一环氧丙烷共聚物中尾一尾，头一尾和头一头结构的存在表明在聚合反应的过程中，α断裂和β断裂相伴发生。稀土三元催化体系对环氧丙烷的开环断裂方式具有一定的选择性，共聚物中头一尾结构的含量高于68mol％。配体的选择和催化剂的组成能够在一定的范围内改变共聚物的规整性。共聚物链段的规整性是影响其玻璃化转变温度的重要因素，聚合物规整性的提高可引起其玻璃化温度的提高；4．稀土三元催化体系能够高效催化二氧化碳一环氧丙烷一氧化环己烯的三元共聚反应。单体的组成影响着二氧化碳共聚物树脂的化学组成和微结构的变化，CHO的引入提高了聚合产物的热稳定性；5．聚丙撑碳酸酷与聚环己撑碳酸醋是不相容的体系，直接在聚丙撑碳酸酯中加入聚环己撑碳酸酯不能改善其热稳定性。

稀土三元催化剂中有机锌对二氧化碳与环氧丙烷共聚反应的影响研究

合成了二乙基锌、二正丙基锌、二正丁基锌、二异丙基锌、二异丁基锌、二仲丁基锌、苯基锌、带基锌、二环己基锌。利用不同有机锌与三氯醋酸钻及甘油组合制备了稀土三元催化剂并催化了二氧化碳和环氧丙烷的共聚合。结果表明当反应温度为80℃，二氧化碳压力为3．0MPa，烷基锌与甘油的摩尔比为2：1，稀土盐与烷基锌的摩尔比为1：20时，利用不同烷基锌制备的稀土三元催化剂的活性均显示较大值。同样聚合条件下，含有支链烷基的烷基锌制备的稀土三元催化剂的活性小于相应的含有同样主链碳原子数的正烷基锌制备的稀土催化剂，对于利用正烷基锌制备的稀土催化剂来说，随着烷基锌中烷基碳原子数的增加，催化活性减小。利用二苯基锌制备的稀土三元催化剂的活性大于利用二乙基锌制备的稀土催化剂。利用酸配和异氰酸酷对二氧化碳和环氧丙烷的共聚物进行了封端，发现封端能显著提高聚合物的热分解温度，改善聚合物的热稳定性。

稀土三元催化剂下二氧化碳/环氧丙烷/缩水甘油醚共聚物的合成与性能研究

为拓宽PPC的应用范围，本论文在CO2与PO的共聚反应中，引入第三单体缩水甘油醚（烯丙基缩水甘油醚AGE、丁基缩水甘油醚BGE和苯基缩水甘油醚GPE），制备得到不同结构和性能的二氧化碳共聚物。主要工作总结如下：1．在CO2与PO的共聚反应中，引入第三单体 AGE，合成了侧链带双键的官能化二氧化碳共聚物Pol（PO-co-CO2-co-AGE）；2．在CO2-PO-BGE的共聚反应中，控制PO／B GE的摩尔比，可制得不同结构和 性能的二氧化碳共聚物Poly（P0-co-CO2-co-BGE），其Tg为-26.8-36.1℃，大幅度拓展了二氧化碳共聚物的最低使用温度区间；3．在CO2与PO的共聚反应中，引入第三单体GPE，合成了侧链带刚性苯环的 二氧化碳共聚物Poty（PO-co-CO2-co-GPE），提高了聚合产物的热稳定性。

QUANTITATIVE-ANALYSIS OF INXGA1-XAS BY AUGER-ELECTRON SPECTROSCOPY

Quantitative Auger electron spectroscopy analysis for the ternary system InGa1-xAs grown by molecular-beam epitaxy has been studied. The relative sensitivity factors are determined by with an internal reference element. The matrix correction factor for In relative to Ga was shown to be 1.08. No preferential sputtering of As for the ternary compounds was found, and the sputter correction factor, K(s)InGa is 0.75. The results are compared with that measured by the x-ray double-crystal diffraction analysis, electron probe microanalysis, and Auger analysis without matrix and sputter corrections.

ELECTRONIC-STRUCTURE OF ND2FE17N

The electronic structures of ternary compound Nd2Fe17N with N atoms on 9e, 3b, and 18g sites are calculated and compared. The local moments on different Fe sites are in good agreement with experiments. The mechanism of increasing Curie temperature by N doping is checked by additional calculations with lattice expansion. The results show that the change in interatomic interaction is more important than the lattice expansion effect.

GROWTH OF WIDE-BAND GAP IMMISCIBLE II-VI ALLOYS BY METALORGANIC VAPOR-PHASE EPITAXY

Although metalorganic vapor phase epitaxy (MOVPE) is generally regarded as a non-equillibrium process, it can be assumed that a chemical equilibrium is established at the vapor-solid interface in the diffusion limited region of growth rate. In this paper, an equilibrium model was proposed to calculate the relation between vapor and solid compositions for II-VI ternary alloys. Metastable alloys in the miscibility gap may not be obtained when the growth temperature is lower than the critical temperature of the system. The influence of growth temperature, reactor pressure, input VI/II ratio, and input composition of group VI reactants has been calculated for ZnSSe, ZnSeTe and ZnSTe. The results are compared with experimental data for the ZnSSe and ZnSTe systems.

Exciton Localization and Delocalization in GaNAs/GaAs Quantum Wells

We have studied exciton localization and delocalization effect in GaNAs/GaAs quantum wells (QWs) grown by molecular beam epitaxy (MBE) using photoluminescence (PL) and timeresolved PL measurements. Studied results suggest that, at low temperature and under a conventional CW excitation, measured PL spectra were dominated by localized exciton (LE) emission caused by potential fluctuations in GaNAs layer. However, under short pulse laser excitation, it is different. An extra high-energy PL peak comes out from GaNAs/GaAs QWs and dominates the PL spectra under high excitation and/or at high temperature. By investigation, we have attributed the new PL peak to the recombination of delocalized excitons in QWs. This recombination process competes with the localized exciton emission, which, we believe, constitutes the "S-shaped" temperature-dependent emission shift often reported in ternary nitrides of InGaN and AlGaN in the literature.

热核三分裂以及热核性质的研究

对品字型、拉长双脖型及级联三分裂的位势进行了计算。发现在有限温度下，品字型三分裂与级联三分裂、拉长双脖子三分裂相比，形变位能上并不是最优的。实验测量结果表明热核的能级密度参数是核温度的函数并与核大小有关，或激发能形式的变化。在25MeV/u Ar+Au的对心碰撞中，激发能已接近多重碎裂的“准相变区”

Preparation and characterization of monolithic columns for capillary electrochromatography with weak electroosmotic flow

Monolithic columns of capillary electrochromatography (CEC) with weak electroosmotic flow (EOF) have been prepared by in situ polymerization of butyl methacrylate and ethylene dimethacrylate, without any charged groups in the reaction mixture. The reproducibility of such columns has been proved good no matter whether they are prepared in the same batch or in different batches. In the case of BMA-EDMA monoliths, besides the traditional ternary mixture - 1-propanol, 1,4-butanediol, and water, binary porogenic solvents with only alcohols have also been adopted. Compared with ternary porogenic solvents, the design with binary ones allows for fine control of the pore diameter and the formation of the specific surface of the monolithic polymers. The composition of porogenic reagents has also been shown to have an effect on EOF in the column systems. In addition, the Joule heat effect in such columns has been studied by varying the inner diameter of columns. Through the separation of acidic compounds, monolithic columns with low EOF have shown potential in the analysis of charged samples.

Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x=0, 1 and 2, wt%) alloys

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x = 0, 1 and 2, wt%) alloys heat-treated at 603 K for 2 It have been investigated. T-phase (an Mg-Zn-Nd ternary phase) was observed in the Nd containing alloys. The optimal mechanical properties were obtained in the Mg-4.5Zn-1Nd alloy, and the ultimate tensile strength and yield strength were 228 and 79 MPa, respectively. Through comparing with the Mg-4.5Zn alloy, the increments of ultimate tensile strength and yield strength were 51 and 17 MPa.

Simultaneous electrochemical determination of dopamine, uric acid and ascorbic acid using palladium nanoparticle-loaded carbon nanofibers modified electrode

Palladium nanoparticle-loaded carbon nanofibers (Pd/CNFs) were prepared by electrospinning and subsequent thermal treatment processes. Pd/CNFs modified carbon paste electrode (Pd/CNF-CPE) displayed excellent electrochemical catalytic activities towards dopamine (DA), uric acid (UA) and ascorbic acid (AA). The oxidation overpotentials of DA, UA and AA were decreased significantly compared with those obtained at the bare CPE. Differential pulse voltammetry was used for the simultaneous determination of DA, UA and AA in their ternary mixture.

Simultaneous determination of dopamine, ascorbic acid and uric acid with electrospun carbon nanofibers modified electrode

A novel carbon-nanofiber-modified carbon-paste electrode (CNF-CPE) was employed for the simultaneous determination of dopamine (DA), ascorbic acid (AA) and uric acid (UA) with good selectivity and high sensitivity. The CNFs were prepared by combination of electrospinning technique with thermal treatment method and were used without any pretreatment. In application to determination of DA, AA and UA in the ternary mixture, the pristine CNF-CPE exhibited well-separated differential pulse voltammetric peaks with high catalytic current. Low detection limits of 0.04 mu M, 2 mu M and 0.2 mu M for DA, AA and UA were obtained, with the linear calibration curves over the concentration range 0.04-5.6 mu M, 2-64 mu M and 0.8-16.8 mu M, respectively.

The copolymerization of carbon dioxide and propylene oxide with Y(CCl3COO)(3)-diphenylzinc-glycerol catalyst

Various organometallic compounds (diphenylzinc, dibenzylzinc, dicyclohexylzinc, bis( pentafluorophenyl) zinc, diethylzinc, di(n-butyl) zinc, triethylaluminum) were used to form Y(CCl3COO)(3)-organometallic compound-glycerol catalyst for the copolymerization of carbon dioxide and propylene oxide. It was found that Y(CCl3COO)(3)-diphenylzinc-glycerol catalyst showed the highest catalytic activity, at optimum conditions the yield could be as high as 478.8 ( g polymer/mol Zn h).

Electrolytic Deposition and Diffusion of Lithium onto Magnesium-9 Wt Pct Yttrium Bulk Alloy in Low-Temperature Molten Salt of Lithium Chloride and Potassium Chloride

The electrolytic deposition and diffusion of lithium onto bulk magnesium-9 wt pct yttrium alloy cathode in molten salt of 47 wt pct lithium chloride and 53 wt pct potassium chloride at 693 K were investigated. Results show that magnesium-yttrium-lithium ternary alloys are formed on the surface of the cathodes, and a penetration depth of 642 mu m is acquired after 2 hours of electrolysis at the cathodic current density of 0.06 A center dot cm(-2). The diffusion of lithium results in a great amount of precipitates in the lithium containing layer. These precipitates are the compound of Mg41Y5, which arrange along the grain boundaries and hinder the diffusion of lithium, and solid solution of yttrium in magnesium. The grain boundaries and the twins of the magnesium-9 wt pct yttrium substrate also have negative effects on the diffusion of lithium.