MgCl2/Et3N Base System as a New Catalyst for the Synthesis of α‐Hydroxyphosphonate

An efficient and simple synthesis of α‐hydroxyphosphonates via reaction of aldehydes and ketones with dimethylphosphite in the presence of MgCl₂/Et₃N base system is reported. The use of readily available and easy to handle reagent MgCl₂/Et₃N makes this method simple, convenient, and practical.     

Detitanation of MgCl2‐supported Ziegler‐Natta catalysts for the study of active sites organization

Thermal treatments under vacuum of conventional supported Ziegler‐Natta precatalysts (MgCl₂/TiCl₄/Dibutylphthalate) were conducted to gradually remove titanium to modify the active sites distribution. Only limited detitanations of precatalysts were achieved paying attention not to chemically alter the internal donor (T < 150 °C). Used in combination with the required cocatalyst and external donor in the propylene slurry polymerization, the modified precatalysts exhibited a drop of activity versus decreasing titanium content but the distributed polymer properties are almost not affected (a slight narrowing of molecular weight distribution was observed). After a titanium chloride secondary impregnation (possibly done in presence of an additional Lewis base), activity resumed but polymer properties are once again unchanged. These findings highlight the difficulty to separate the different families of active sites and lead us to propose a cluster organization of titanium active sites. Active sites are composed of titanium clusters having a size distribution at the precatalyst surface, possessing a critical operating size and operating collectively in polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5461–5470, 2008     

Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

Ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

Data on ethylene polymerization over supported LFeCl₂/MgCl₂ catalysts {L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl]pyridyl} containing AlR₃ (R = Me, Et, i‐Bu, or n‐Oct) as an activator are presented. These catalysts are highly active (100–300 kg of polyethylene/g of Fe h bar of C₂H₄) and stable in ethylene polymerization at 70–80 °C. Data on the effects of the iron content, AlR₃ type, Al(i‐Bu)₃ concentration, and hydrogen presence on the catalyst activity are presented. The molecular structure of polyethylene produced with these catalysts (including the molecular masses, molecular mass distribution, branching, and number of C?C bonds) has been studied; data on the effects of AlR₃ and hydrogen on the molecular structure are presented. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2128–2133, 2005     

Theoretical study of the potential energy curves of the diatomic radicals MeIIX. III. Application to MgCl,CaF and CaCl radicals and some preliminary remarks

The series of calculations of the potential energy curves of the diatomic radicals Me_IIX (Me_II = second group metal, X = halogen), has been extended to MgCl, CaF and CaCl. The calculations have been performed according to a stepwise procedure, outlined in previous works. The presently available results allow comparisons for the first members of the series.     

Establishment of de facto standard catalysts in the polypropylene industry

Polypropylene (PP) has become an indispensable material in our daily lives. Annual worldwide production of PP is now more than 30000000 tons and is predicted to grow at an annual rate of about 6% during the first decade of the 21st century. Commercial production of PP began in 1957 with the use of TiCl(3) catalysts established by Ziegler and Natta. However, the low activities and low stereospecificities of the catalysts resulted in large amounts of catalyst residue and atactic PP in the product, necessitating steps for their removal in commercial production. As a means of finding appropriate catalysts, we developed MgCl(2)-supported TiCl(4) catalysts, which basic concept was introduction of organic compounds onto the inorganic crystal catalyst surface. This addition led to remarkable enhancements in stereospecificity with extremely high activity. Use of the new catalysts enlarged and simplified the PP production process by eliminating the steps previously required for removal of catalyst residue and atactic PP. In addition, it greatly improved the properties of the PP, enabling a much wider range of PP applications by replacing metal and engineering plastics with the highly stereoregular PP. Therefore, these catalysts helped the rapid establishment of the current PP industry and now play a major role in production. The latest MgCl(2)-supported TiCl(4) catalyst is providing precise control of the isotactic PP structure. Future expectations for this type of catalyst are to acquire a single-site nature and to contribute to the creation of a new class of hybrid materials.     

MgCl_2晶型对丙烯聚合MgCl_2载体催化剂活性的影响

ＭｇＣｌ_２晶型对丙烯聚合ＭｇＣｌ_２载体催化剂活性的影响张明辉，肖世镜中国科学院化学研究所，北京，１００８０）关键词丙烯聚合、ＭｇＣｌ２、载体催化剂近年来，有关ＭｇＣＩ。载体催化剂的研究报道和综述文章不少，但涉及载体晶型对催化剂结构性能的影响却少见．...     

用于制备齐格勒-纳塔催化剂的氯化镁载体

氯化镁载体型齐格勒-纳塔催化剂具有高活性、聚合物形态可控等优点,是目前聚烯烃工业中最普遍使用的催化剂。氯化镁载体是此类催化剂的主要组份之一,对载体型齐格勒-纳塔催化剂的研发具有重要意义。氯化镁载体制备技术是氯化镁载体型齐格勒-纳塔催化剂研发的关键技术之一。本文简要介绍了载体型齐格勒-纳塔催化剂的发展历程,从氯化镁的结构出发分析了氯化镁作为载体的优势,重点介绍了氯化镁载体制备的关键技术:氯化镁活化方法和载体形态控制方法,尤其是球形氯化镁载体的成形技术。     

给电子体在丙烯聚合MgCl2载体催化剂体系中的作用

制备了3种含有不同内给电子体(邻苯二甲酸二异丁酯,9,9-二甲氧基甲基-芴和1,1-双甲氧基甲基-环丁烷)的MgCl2负载型丙烯聚合齐格勒-纳塔(Z-N)催化剂,研究了给电子体结构与聚合性能之间的关系,用红外光谱剖析了催化剂及其相关化合物的结构,结果发现催化剂中的内给电子体直接与MgCl2配位,而没有与TiCl4结合.内给电子体的加入,降低了Z-N催化剂中钛的含量,提高催化丙烯聚合的活性,使聚合物的分子量分布变窄.聚合物立构规整度的变化强烈依赖于内给电子体的结构.     

Effect of different donors on kinetics of Zn catalysts and molecular weight of the obtained polypropylene

This paper studies MgCl₂/internal donor/TiCl₄//external donor/AlEt₃ catalytic systems where ethyl benzoate (E.B.) or 2,2,6,6 tetramethylpiperidine (TMPiP) are used as internal and external donors. E.B. as external donor does not change the molecular weight of the product with TMPiP as internal donor. The molecular weight of polypropylene decreases drastically and global productivity and stereoselectivity are very low with MgCl₂/internal Donor/TiCl₄//external donor/AlEt₃ when TMPiP is the external and internal donor. In this case the insoluble fraction in n-heptane is highly stereospecific and the molecular weight is similar to commercial products. We present a new explanation of these results, based on Ystenes proposal, comparing both precatalysts.