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It is demonstrated that the chiral quaternary ammonium salts catalysts exhibit promising catalytic properties for the substrate. Part III: The synthesis and the characterizing of the macroporous aminomethyl resin-supported cinchona alkaloid complexes and the study on its catalytic properties The part consists of two subsections. the macroporous aminomethyl resin -supported cinchona alkaloid complexes were synthesized by the stuff (cinchonine, quinine and macroporous aminomethyl resin). Their structures were characterized by means of elemental analysis, XPS, TG/DTA; the chiral polymer-supported complexes were first used as catalysts for the reduction of ketones. Their catalytic properties for the reduction processes were investigated. The comparison of the products e.e., the conversion of the substrate among different reduction processes was employed with determined by HPLC. The effects of the time, the temperature, the ratio of catalyst to substrate, reaction solvent as well as the recycle times were also discussed.

第三章聚-4-氨甲基苯乙烯负载金鸡纳碱金属络合物的合成与表征及其不对称催化性能研究本章分为两节,以辛可宁和奎宁及聚-4-氨甲基苯乙烯为原料,合成了4种聚-4-氨甲基苯乙烯负载金鸡纳碱络合物催化剂,并对它们的结构用元素分析、X-射线光电子能谱、TG/DTA等几种测试手段进行了表征;首次将所合成的手性高分子负载的金属络合物用于催化芳香酮不对称还原反应,详细研究了所得的手性高分子负载的金属络合物对不同底物的催化性能,用HPLC等分析手段定量检测了还原过程的底物转化率及其产物对映异构体选择性,并考察了反应时间、反应温度、催化剂和底物投料比、反应溶剂和循环次数对催化性能的影响。

Study of Optimization DesignThis paper programs three Command Batch Files that can respectively perform optimization designs of 4-point-supported-glass, 6-point-supported-glass and the specially designed 6-point-supported-glass.

这三段命令流可供熟悉ANSYS操作的工程设计人员使用。

Our results reveal that with the same number of cobalt atoms and the same cobalt-substrate interation stength, the melting points and pre-melting intervals of the two kinds of supported Co clusters are all in reasonable agreement with each other. With increasing the depth of supported potential, the melting points increase for the supported cluster. Similar to the case of free clusters, the linear relation between the melting point and the inverse of cluster's size cube root is also found for the two kinds of supported clusters.

结果表明:对于给定原子数目的支撑Co团簇,在衬底势强度相同时,两种衬底势下对支撑团簇熔点及预熔化区间给出了一致的描述;随衬底势强度增加,支撑团簇熔点升高,且两种衬底势所描述的支撑Co团簇也类同于自由Co团簇都表现出较好的熔点与尺寸依赖的线性关系。

New contributions of this work are as follows:(1). Preparation of Spherical MgCl_2-Supported Late-Transition Metal Catalysts for Ethylene PolymerizationFacile and effective immobilization of late-transition metal catalysts. 2,3-bis-(2,6-diisopropylphenyl) butane diimine nickel dibromide (1) and 2,6-bis-[1-(2,4,6-trimethylphenylimino)ethyl]pyridine iron dichloride (2), for ethylene polymerization has been achieved, using spherical MgCl_2 supports obtained by thermal dealcoholization of MgCl_2·2.56C_2H_5OH, and the effects of dealcoholization temperature on supported late-transition metal catalysts and the properties of resultant polymers were studied, the results indicated that:1.Supports with appropriate mechanical strength, high surface area and high porosity could be prepared by thermal dealcoholization of spherical MgCl_2·2.56C_2H_5OH supports; 2.BET, XRD, IR, SEM, GPC and DSC analyses indicate that the activities of the supported late-transition metal catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature.

本工作的新贡献如下:(1)、球形氯化镁负载后过渡金属催化荆催化乙烯聚合本文将配合物2,3-双(2,6-二异丙基苯亚胺)丁烷二溴化镍(1)和配合物2,6-二[1-(2,4,6-三甲基苯亚胺)乙基]吡啶二氯化铁(2)分别直接负载于经不同热脱醇温度处理的球形氯化镁载体上,研究了氯化镁载体的脱醇温度对负载化后过渡金属催化剂及其聚合物的影响,研究表明:1、通过对球形MgCl_2·2.56C_2H_5OH载体进行热脱醇处理,可以获得合适机械强度、较高比表面积和较高孔隙度的球形氯化镁载体;2、BET,XRD,IR,SEM,GPC和DSC研究表明,脱醇温度极大地影响负载后过渡金属催化剂的活性和聚合物的性能。

New contributions of this work are as follows:(1). Preparation of Spherical MgCl_2-Supported Late-Transition Metal Catalysts for Ethylene Polymerization Facile and effective immobilization of late-transition metal catalysts. 2,3-bis-(2,6-diisopropylphenyl) butane diimine nickel dibromide (1) and 2,6-bis-[1-(2,4,6-trimethylphenylimino)ethyl]pyridine iron dichloride (2), for ethylene polymerization has been achieved, using spherical MgCl_2 supports obtained by thermal dealcoholization of MgCl_2·2.56C_2H_5OH, and the effects of dealcoholization temperature on supported late-transition metal catalysts and the properties of resultant polymers were studied, the results indicated that: 1.Supports with appropriate mechanical strength, high surface area and high porosity could be prepared by thermal dealcoholization of spherical MgCl_2·2.56C_2H_5OH supports; 2.BET, XRD, IR, SEM, GPC and DSC analyses indicate that the activities of the supported late-transition metal catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature.

本工作的新贡献如下:(1)、球形氯化镁负载后过渡金属催化荆催化乙烯聚合本文将配合物2,3-双(2,6-二异丙基苯亚胺)丁烷二溴化镍(1)和配合物2,6-二[1-(2,4,6-三甲基苯亚胺)乙基]吡啶二氯化铁(2)分别直接负载于经不同热脱醇温度处理的球形氯化镁载体上,研究了氯化镁载体的脱醇温度对负载化后过渡金属催化剂及其聚合物的影响,研究表明: 1、通过对球形MgCl_2·2.56C_2H_5OH载体进行热脱醇处理,可以获得合适机械强度、较高比表面积和较高孔隙度的球形氯化镁载体; 2、BET,XRD,IR,SEM,GPC和DSC研究表明,脱醇温度极大地影响负载后过渡金属催化剂的活性和聚合物的性能。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area;2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support;3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier;4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling;5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene PolymerizationIn this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that:1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS;2.co-mlling time had no obvious effect on the texture of support after 12 hours;3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现;3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布;4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒;5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明:1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致;2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响;3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area; 2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support; 3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier; 4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling; 5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene Polymerization In this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that: 1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS; 2.co-mlling time had no obvious effect on the texture of support after 12 hours; 3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现; 3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布; 4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒; 5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明: 1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致; 2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响; 3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

Three kinds of ionic liquid were used to support the acetylacetone at the C3 position directly according to the method indicated above. These synthesized ionic liquid supported acetylacetone catalysts include imidazolium salts ionic liquid supported acetylacetone catalysts, pyridinium salts ionic liquid supported acetylacetone catalysts and ammonium salts ionic liquid supported acetylacetone catalysts. All these catalysts were characterized by ~1H-NMR,~(13)C-NMR, IR and elementary analysis.

采用设计过程中预期能够提高乙酰丙酮金属催化剂催化氧化活性的修饰方式,合成了三类离子液体支载的乙酰丙酮金属催化剂:咪唑型离子液体支载乙酰丙酮金属催化剂、吡啶型离子液体支载乙酰丙酮金属催化剂、胺型离子液体支载乙酰丙酮金属催化剂,并采用核磁共振氢谱、碳谱,红外光谱及元素分析来对这些新型的催化剂进行了表征。

With the development of modern communication networks and computer application technology, more and more attentions are paid to the CSCW (Computer Supported Cooperative Work) study field, which orients to multi-user cooperation.

随着现代通信网络和计算机应用技术的发展,面向多用户协同的计算机协同工作(Computer Supported Cooperative Work,CSCW)研究领域越来越引起科研人员的关注。

New box design with durable 0.5 inch (13 mm) paving skin Vertically-adjusting mold mount for precise leveling of mold to machine Telescoping end sections with 12 inches (305 mm) of width variation on each side are available Standard paving depth is zero to 24 inches (610 mm)Edge slump adjustment Hydraulic Vertical Hinged Sideplates, self-contained inside the mold for track clearance Split, pressure-compensated sideplates Folding side plate wings for transporting without removing Pivoting mold mounting beam to eliminate stress points Self-supported TA is hydraulically driven with 3.5 inch (89 mm) ACME screws for up to a six inch (152 mm) crown Front and rear top T-bar on mold for attaching accessories and structural integrity Inserts are bolted together with front and rear alignment pins for easy mold assembly New vibrator mounting tube attaches to T-bar on mold – Vertical vibrator lift – Rear lubrication system with grease zerks accessible from the work bridge New strike-off – Mounted on paver frame T-rail, independent of the mold – New modular design with wedge lock system for ease in changing widths – 10 inches (254 mm) of hydraulic height adjustment – Hydraulic crown adjustment Spreader plow mounted to paver frame T-rail, optional auger available Tamper bar optional

与耐久性的新的箱子设计铺精密水准测量的0.5英寸(13 mm)皮肤垂直调整的模子登上模子用机器制造挤撞与12英寸(305 mm)的末端部分在每边的宽度变异是可利用的标准铺的深度是零对24英寸(610 mm)边缘暴跌调整水力垂直的取决于的Sideplates,独立性在轨道清除分裂的模子里面,折叠运输的pressure-compensated sideplates旁边板材翼没有去除在轴上旋转的模子架置射线消灭重音点Self-supported TA水力驾驶与3.5英寸(89 mm)由六英寸(152 mm)冠决定的尖端螺丝在前后冠上在模子的T酒吧附有的辅助部件并且结构正直插入物与容易的模子汇编新的振荡器架置管随员T酒吧的定位销一起在前后被闩上在模子–垂直的振荡器推力与油膏zerks的–后方润滑系统容易接近从新工作的桥梁触击–在摊铺机框架足迹,模子的独立登上了与楔子锁系统的–新的模块设计在改变的宽度的舒适的– 10英寸(254 mm)水力高低调整–水力冠调整分布器犁登上了对摊铺机框架足迹,任意任意木钻可利用的堵塞器的酒吧

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But in the course of internationalization, they meet with misunderstanding and puzzlement.

许多企业已经意识到了这一点,但在国际化的进程中,仍存在一些误区与困惑。

Inorder toaccomplish this goal as quickly as possible, we'll beteamingup with anexperienced group of modelers, skinners, and animatorswhosenames willbe announced in the coming weeks.

为了尽快实现这个目标,我们在未来数周内将公布与一些有经验的模型、皮肤、动画制作小组合作。

They answered and said to him, Are you also from Galilee?

7:52 他们回答他说,难道你也是出于加利利么?