球形MgCl2载体催化剂催化乙烯聚合

考察了球形MgCl2载体催化剂在乙烯聚合过程中的催化性能和动力学行为,分析了聚合过程的传热、传质和温度、聚合压力对催化剂行为的影响。聚合温度在30～80℃和乙烯压力在0．12～0．72MPa时,随着温度和压力的提高,聚合活性增加,聚合物堆密度由0．27g/cm^3降低至0．22g/cm^3。     

加氢条件下球形MgCl2载体催化剂催化乙烯聚合

为开发可控制形态的催化剂并表征其在乙烯聚合过程中对氢气的响应,测定了不同氢气加入量条件下球形MgCl_2载体催化剂在乙烯聚合过程中的活性及聚合物的相对分子质量等。研究发现,随着氢气加入量的增加。氢气对第二活性中心的化学毒化加剧,催化剂活性明显降低。通过对聚合物相对分子质量和氢气分压的关联,认为氢气是通过吸附解离形成原子氢,利用氢气可对聚合物的熔体流动速率在0.2～10.0g/10min进行调节。     

球形MgCl2载体催化剂催化1-丁烯聚合

在以三乙基铝(AlEt3)为助催化剂、n(Al)/n(Ti)为300、聚合压力为0.10 MPa、聚合温度为30℃、通入氢气3 mL、环己基甲基二甲氧基硅烷(CHMMS)与Al的摩尔比为0.033、聚合2h的条件下,球形MgCl2载体催化刺的活性为607g/g,聚1-丁烯的等规指数为82.3%.依催化剂活性大小,外给电...     

非均相乙烯聚合催化剂载体研究新进展

文章介绍了近年来聚乙烯催化剂载体的研究情况,着重介绍了无机载体,粘土载体,分子筛载体,高分子载体的研究现状。无机载体主要集中于提高载体酸度,及其向纳米载体方向发展,粘土作为聚乙烯催化剂载体可以有效的改性聚合物的力学性能,可以制备高性能复合材料,MCM-41,SBA-15,ZSM-5等分子筛载体展示出了比SiO2作为载体更好的催化活性,增加载体的酸性会明显的提高活性,有序排列的大孔道结构将会更有利于活性中心的负载和乙烯的聚合反应。有机化合物类高分子载体由于不需要对载体本身进行预处理也受到越来越多的重视。     

有机铬催化剂催化乙烯聚合

研究了有机硅烷铬酸酯催化剂(简称有机铬催化剂)在乙烯气相均聚合小试中的催化性能和聚合动力学行为。考察了不同种子床制备方法、有机铬催化剂加入量、聚合温度、乙烯与氢气分压比对聚合的影响,并对聚乙烯(PE)进行了结构与性能的分析表征。结果表明:经热活化与化学活化处理后的硅胶表面基本不含羟基,适宜作为种子床使用;有机铬催化剂加入量在100.0~150.0 mg时其活性最高且保持稳定,聚合动力学曲线为快速上升缓慢下降型;聚合温度在80~100℃时有机铬催化剂活性最高且变化不大,但在110℃时下降;随聚合温度升高,PE的重均分子量与数均分子量均降低,且相对分子质量分布明显变窄;H2的加入会显著降低有机铬催化剂活性。     

MgCl2-BuOH/TiCl4催化剂催化乙烯聚合

研究了自制MgCl2-BuOH/TiCl4催化剂在不同条件下用于乙烯均聚合和共聚合的性能,考察了不同的氢气分压、铝钛摩尔比和共聚单体浓度对催化剂活性和聚合反应动力学的影响,测试了聚合产品的熔体流动速率、堆密度及拉伸性能等,表征了聚合产品的相对分子质量及其分布、分子链结构,得出了聚合条件对MgCl2-BuOH/TiCl4催化剂及其产品性能影响的一般规律.     

后过渡金属催化剂催化乙烯聚合

考察了不同温度,Ａｌ／Ｆｅ比以及催化剂浓度等条件下后过渡金属ＦｅＭＡ催化剂乙烯常压聚合的催化活性和动力学行为。     

乙烯聚合双功能催化剂概述

乙烯在一个以应器中同时进行齐聚和共聚反应的新工艺,是近年来乙烯聚合研究领域中的热点之一,本文以混合型有机铬／氧化铬催化剂和钛系催化剂为例,介绍了乙烯聚合双功能催化剂的制备方法,技术特点,聚合动力学以及所合成树脂的性能等,综述了该研究领域的一些新进展,并对两种不同类型的双功能催化进行了简单评述。     

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.     

一种乙烯聚合用TiCl_4/MgCl_2催化剂的制备

研究了含Mg载体ClMg(OR)·ROH(R为乙基和正丁基)的制备和反应机理。分别以CH2Cl2,CHCl3,CCl4作为溶剂,在n(C2H5OH)/n(Mg)为2.0的条件下,可以合成ClMg(OC2H5)·C2H5OH载体,并且成本较低。采用ClMg(OR)·ROH为载体与TiCl4反应,制备了乙烯聚合用负载型催化剂,研究了该催化剂的制备规律和催化乙烯聚合的性能。结果表明:以ClMg(OC4H9)·C4H9OH为载体制备TiCl4/MgCl2催化剂,载Ti时间为2 h,载Ti温度为110℃,TiCl4用量为2.0 mL/g,载Ti次数为3次时,制备的负载型催化剂催化乙烯聚合具有较高的活性,可达4.6 kg/(g·h)。     

新型MgCl_2负载钛催化剂在丙烯聚合中的应用

用优化乳化法制备了MgCl_2负载钛催化剂,考察了催化剂的形态结构并将其应用于丙烯催化聚合。聚合温度70℃、氢气加入量为1 L,采用二异丁基二甲氧基硅烷作为外给电子体时,催化剂具有较高的催化活性,同时聚丙烯具有较高的等规指数。     

Ethylene polymerization catalyzed by metallocene supported on mesoporous materials

Summary  In this work, different mesoporous materials were employed for the preparation of supported metallocene catalysts to be evaluated in ethylene polymerization and their performance was related to the chemistry of the materials surface used as support. The supports employed were MCM-41, SBA-15 and mesoporous TiO₂. The performance of the prepared catalysts was compared with the homogeneous catalyst precursor system. Those mesoporous materials, as well as the prepared metallocene catalysts, were analyzed by infrared absorption spectrometry (FTIR). Polymers were also characterized by FTIR, for the determination of the number-average molecular weight, and by differential scanning calorimetry (DSC) to determine thermal characteristics of the produced polyethylene. Among the studied metallocene supported catalysts, the one based on the mesoporous support SBA-15 achieved the highest activities, almost as high as that observed for the homogeneous system.     

Ethylene polymerization using a novel MgCl2/SiO2‐supported Ziegler–Natta catalyst

A novel MgCl₂/SiO₂‐supported Ziegler–Natta catalyst was prepared using a new one‐pot ball milling method. Using this catalyst, polyethylenes with different molecular weight distributions were synthesized. The effects of the [Si]/[Mg] ratio, polymerization temperature and [Al]/[Ti] ratio on the catalytic activity, the kinetic behaviour and the molecular weight and the polydispersity of the resultant polymer were studied. It was found that the polydispersity index of the polymer could be adjusted over a wide range of 5–30 through regulating the [Si]/[Mg] ratio and polymerization temperature, and especially when the [Si]/[Mg] ratio was 1.70, the polydispersity index could reach over 25. This novel bi‐supported Ziegler–Natta catalyst is thus useful for preparing polyethylene with a required molecular weight distribution using current equipment and technological processes. Copyright © 2005 Society of Chemical Industry     

Study of propylene polymerization catalyzed by a spherical MgCl2‐supported Ziegler–Natta catalyst system: The effects of external donors

Spherical MgCl₂‐supported Ziegler–Natta catalysts containing internal donors, such as diethyl phthalate, diisobutyl phthalate, and di‐n‐octyl phthalate, have been prepared. The effects of external donors, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxylsilane, on the propylene polymerization catalyzed by these catalysts were studied. The results indicate that the external donors not only led to an increase in the isotactic index, but also affected the morphology of resultant polymer particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 738–742, 2005     

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.

High temperature polymerization of propylene catalyzed by MgCl2‐supported Ziegler–Natta catalyst with various cocatalysts

Four cocatalysts, referred to as ethylaluminoxanes, were synthesized by the reaction between triethylaluminium (AIEt₃) and water under various molar ratios of H₂O/Al at ?78°C. Aluminoxanes were used as cocatalysts for a MgCl₂‐supported Ziegler–Natta catalyst for propylene polymerization at temperatures ranging from 70 to 100°C. When the polymerization was activated by AlEt₃, the activity as well as the molecular weight and isotacticity of the resulting polymer gradually dropped as the temperature varied from 70 to 100°C. When ethylaluminoxane was employed as the cocatalyst, good activity and high molecular weight and isotacticity were obtained at 100°C. Furthermore, when the cocatalyst varied from AlEt₃ to ethylaluminoxane, the atactic fraction and polymer fraction with moderate isotacticity decreased and the high isotactic fraction slightly increased, which indicated that the variation of the cocatalyst significantly affects the isospecificity of active sites. It was suggested that the reactivity of the Al‐Et group and the size of the cocatalyst were correlated to the performance of the Ziegler–Natta catalyst at different temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1978–1982, 2006