茂金属烯烃聚合催化剂 V.茂金属催化剂多相化研究

介绍了茂金属化合物及其他活性中心催化剂负载于SiO2、MgCl2、沸石、高分子材料等多种不同的载体上合成载体催化剂的研究，以及茂金属催化剂用于烯烃聚合反应的特征。     

茂金属烯烃聚合催化剂Ⅲ.乙烯聚合茂金属催化剂结构和配体对聚合反应的影响

介绍了茂金属催化剂的研究进展及茂金属催化剂在乙烯,丙烯和苯乙烯等聚合反应中的应用。     

茂金属均相催化剂研究进展

综述了用于烯烃聚合的茂金属均相催化剂的合成、影响催化性能的因素和催化作用机理,重点介绍了非桥连结构和桥连结构茂金属均相催化剂的催化行为。     

茂金属催化剂的研究进展

介绍了茂金属催化剂合成技术,重点阐述了非桥联型、桥联型、限定几何构型、离子型和负载型茂金属催化剂的合成、结构及性能。     

烯烃聚合用Z-N催化剂活性中心的影响因素及研究方法

综述了烯烃聚合用Ziegler-Natta(Z-N)催化剂活性中心的影响因素以及基于活性中心浓度测定的聚合动力学研究方法。内给电子体对催化剂的载Ti量和Ti分布以及Mg Cl2载体的微晶结构和形态都有重要影响;外给电子体的毒化作用使活性中心浓度下降,但无规活性中心浓度的下降幅度更明显,因而等规活性中心比例相对升高;共聚单体的加入使催化剂颗粒破碎,从而暴露出新的活性中心,增加了活性中心的浓度;加入氢气后聚合反应速率显著提高。由于Z-N催化剂的结构和反应机理高度复杂,研究其微观机理仍面临很多瓶颈。     

Kinetic study of olefin polymerization with a supported metallocene catalyst. III. Ethylene homopolymerization in slurry

A kinetic study of ethylene homopolymerization is conducted with a supported unbridged metallocene catalyst in a slurry reactor. The effects of operational parameters such as the reaction temperature and pressure on kinetics are investigated. The kinetic parameters which have been determined for this particular catalyst from previous gas phase studies are used in a slurry reactor model to predict the polymerization behavior under various reaction conditions. The experimental data compare favorably with the predictions from this model. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2901–2917, 2001     

Kinetic study of olefin polymerization with a supported metallocene catalyst. IV. Comparison of bridged and unbridged catalyst in gas phase

A kinetic study of ethylene/1‐hexene (E/1‐H) copolymerization is conducted with a supported bridged metallocene catalyst in a gas phase reactor. The investigation into the kinetics of ethylene/1‐hexene copolymerization includes the effects of operational parameters such as the reaction temperature, pressure, and comonomer concentration. On‐line perturbation techniques are implemented to determine key kinetic parameters such as the activation energies for propagation and catalyst deactivation. A comparison of the kinetic parameters and behavior is made between the bridged and a previously studied unbridged catalyst. Finally, a two‐site model is proposed to explain the observed kinetic behavior with changing reaction temperature and comonomer concentration. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1451–1459, 2001     

Acidic lamellar aerogel nanoplate activated olefin polymerization with metallocene catalysts

Acid lamellar aerogel (HLA) with charge delocalized across the layer surface demonstrated very high efficiency in activating metallocene complexes when combined with aluminum alkyls for olefin polymerization. The activation mechanism was also investigated.     

Kinetic study of olefin polymerization with a supported metallocene catalyst. I. Ethylene/propylene copolymerization in gas phase

A kinetic study of ethylene homopolymerization and copolymerization is conducted with a supported metallocene catalyst in a gas‐phase reactor. An experimental procedure is developed that minimizes the effect of impurities in the reactor and simultaneously yields consistent and reproducible reaction‐rate data. The effects of operational parameters such as reaction temperature, pressure, and comonomer concentration on the kinetics of both homopolymerization and copolymerization are investigated. Online perturbation techniques are implemented to determine key kinetic parameters such as the activation energies for ethylene propagation and catalyst deactivation. A reaction‐rate order close to 2 is obtained for ethylene homopolymerization from pressure perturbations, while near to first‐order dependency is observed in the presence of propylene. To quantify the effects of the operational parameters, a one‐site kinetic model for homopolymerization and a two‐site kinetic model for copolymerization are proposed. The necessary kinetic parameters in the model are estimated using the POLYRED™ package. The resulting kinetic model represents the kinetic data over a wide range of conditions for this supported metallocene catalyst. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 81–114, 2001     

采用Z-N/茂金属复合催化剂制备PP釜内合金

制备了Ziegler-Natta/茂金属(Z-M)复合催化剂,用Z-M复合催化剂采用一段丙烯本体均聚合、二段乙烯-丙烯气相共聚合制备了聚丙烯(PP)釜内合金PPc-A.与采用传统Ziegler-Natta催化剂ZN118制备的抗冲聚丙烯釜内合金SP179对比,两合金具有相近的熔体流动速率及乙烯含量,但冲击强度相差较大....     

丙烯聚合Z-N催化剂中的给电子体及其作用机理

综述了近年来在新型给电子体方面的研究进展。给电子体作用机理的研究需要测试技术和表征手段的进步。对机理的研究是Ziegler-Natta(Z-N)催化剂领域研究的核心,将为新型给电子体的开发指明方向,同样也是Z-N催化剂发展的方向。     

Ziegler-Natta/茂金属复合催化剂制备双峰聚乙烯

通过把茂金属催化剂负载在Ziegler-Natta催化剂上制备了ZM复合催化剂,在单一聚合反应器内研究了ZM催化剂用于乙烯聚合制备双峰聚乙烯的性能。考察了催化剂中茂金属化合物的含量、聚合过程中反应温度、助催化剂的用量和共聚单体1-己烯的用量对催化剂乙烯聚合性能的影响规律。结果表明：采用ZM催化剂可以在单反应器内催化乙烯聚合得到分子量分布呈双峰的聚乙烯,聚乙烯的分子量分布达到155,聚合活性可达2.52×10⁷ g/molMt·h。     

Ethylene polymerization on polymer supported Ziegler-Natta catalyst

Poly(styrene-co-methyl methacrylate) has been used as a support for titanium based Ziegler?CNatta catalyst. We have prepared three polymer supported catalysts by varying the weight ratio of TiCl₄ and polymer to perform the ethylene polymerization. Triethylaluminium (TEA) is used as cocatalyst. Catalysts have been characterized by XPS, FT-IR, UV-visible spectroscopy, XRD, pH meter, TGA and SEM-EDX. The catalysts are found to be stable upto 100?°C. Density functional theory (DFT) has been used to elucidate the structure of TiCl₄ and the polymer supported complex. All these spectroscopic analysis and density functional study confirm the incorporation of titanium into the polymer matrix. The catalytic activity is found to be in the range of 0.6?C1.01?kg of polyethylene (PE)/g Ti/h and the catalytic activity depends on the optimum level of Ti content. The molecular weight ( $ \overline {{M_w}} $ ) of PE is in the range of 237,300?C275,600?g/mol. Present study also reports the stability and storability of the catalysts.

Electrochemically assisted ethylene (co-)polymerization with a vanadium-based Ziegler-Natta catalyst

A facile and efficient electrochemically assisted ethylene polymerization and ethylene-propylene copolymerization with the widely used VOCl₃/ethylaluminum sesquichloride (EASC) catalyst system was demonstrated. The low-activity and/or inactive low-valence-state V species present in the catalyst were oxidized to high-valence-state V through electrochemical methodology. Thus, the catalytic activity of the VOCl₃/EASC catalyst system was significantly improved. The effects of electrochemical application on the resultant polymer structure and properties were investigated. This work provides a new strategy to improve the performance of Ziegler-Natta catalysts.     

烯烃聚合用茂金属催化剂负载化机理的研究进展

从无机载体、有机高聚物载体和有机无机杂化高聚物载体催化剂三方面综述了近年来烯烃聚合用茂金属催化剂负载化的研究进展。与多活性中心催化剂相比,茂金属催化剂具有活性高,用其所制聚合物的相对分子质量分布窄等特点,茂金属催化剂负载化克服了用均相催化剂制备的聚合物形貌不可控的缺点,并可降低助催化剂用量。目前无机载体是工业生产中最常用的载体类型,但用高聚物载体负载所具有的不需要复杂预处理、茂金属催化剂易被官能化及产物中载体成分不影响最终催化剂性能等优点,也逐渐受到关注。     

茂锆金属催化剂催化乙烯聚合研究

主要考察了含锆的茂金属催化剂中催化乙烯反应条件优化研究,在最优条件下催化聚合反应所得的产物与吉林石化公司聚乙烯厂聚乙烯产品进行分析对比.对茂锆金属催化剂催化乙烯聚合反应条件研究表明,适宜的助催化剂[Al]与主催化剂[Cat]的摩尔比在1 500左右,适宜的主催化剂浓度在1.5×10-4 mol/L左右,最佳聚合温度60℃,此时催化剂的活性可达到106 gPE/(molCat·h).从物理性能、热性能、相对支化度、相对分子质量及其分布分析可知,制备出的负载茂锆金属催化剂在最优反应条件下催化乙烯聚合所得的产物与吉林石化公司聚乙烯产品性质基本一致,符合产品的指标,支链分布均匀,分子量分布更窄.同时对茂锆金属催化剂主、助催化剂催化乙烯聚合的作用和机理进行了探讨.     

Propylene polymerization in a semibatch reactor. Analysis of soluble metallocene catalyst behavior through reactor modeling

We study the process involved in metallocene activation and further propylene polymerization. In this paper, we begin by analyzing the behavior of soluble metallocene in propylene polymerization before advancing to the study of the heterogeneous polymerization. Experimental data obtained in a semibatch laboratory polymerization reactor using ethylenbisindenylzirconium dichloride (EtInd₂ZrCl₂)/ methylaluminoxane (MAO) are combined with a mathermatical model providing useful information such as number of active sites and their activation patterns. We present a mathematical model for the reactor that predicts not only reactor productivity but also the molecular properties of the product. We apply the model to soluble systems in order to find the optimal parameters for the catalyst itself and in the presence of different types of additives such as aluminum chloride (AlCl₃) and ethyl benzoate (E.B.).     

铁系聚烯烃催化剂的合成及其应用

合成了2类铁系聚烯烃催化剂(常规铁系催化剂及树枝状铁系催化剂).评价了这两类催化剂在丙烯聚合中的催化效果.结果表明:在温度20℃、n(Al)/n(Fe)为1 000时,常规铁系催化剂的催化活性为137 kg,(mol·h),楔形树枝状铁系催化剂聚合活性为163 kg/(mol·h),聚合物的数均分子量也提高到1×104以上,等规指数约为76%.     

Polymer-supported heterogeneous titanium-based Ziegler-Natta catalyst for ethylene polymerization

Reported here in, is the synthesis of polystyrene (PS)-supported Ziegler–Natta catalyst (PS-TiCl₄) by the reaction of PS and titanium tetrachloride (TiCl₄). PS was synthesized by emulsion polymerization using super critical CO₂ (sc-CO₂) as a medium. Three catalysts were synthesized by varying the TiCl₄/PS weight ratio in hexane medium. The resulting catalysts were characterized by Fourier transformed-infrared spectroscopy, UV–visible spectroscopy, scanning electron microscope and energy dispersive X-ray detector, X-ray diffraction analysis. The acidity of the catalysts in an acetone/water solution was measured by pH meter. The thermogravimetric analysis reveals that catalysts are stable upto 150–180°C. Due to their higher degree of thermal stability these catalysts may potentially be used as a support in conventional Ziegler–Natta catalyst for ethylene polymerization. These catalysts also showed good storability and its overall catalytic productivity are found to be 3720 g PE/g Ti. The productivity of the catalysts also depended on the titanium concentration in the polymer matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012