乙烯聚合Phillips型铬系催化剂研究进展

Phillips型铬系催化剂由于制备工艺简单,聚合过程不使用任何助催化剂,广泛应用于乙烯聚合,对世界聚烯烃工业的发展具有重要的推动作用。主要从Phillips型铬系催化剂的发展历程、催化剂制备与结构和聚合产品特性方面进行综述,并指出今后我国铬系催化剂的研发方向。     

铬系乙烯聚合催化剂研究进展

介绍了铬系乙烯聚合催化剂的类型、改性与发展。指出需对该类型催化剂的聚合反应机理作进一步研究。     

乙烯聚合铝改性铬系催化剂研究进展

综述国内外乙烯聚合铝改性铬系催化剂的研究现状、制备方法、性能以及对乙烯聚合性能的影响。铝改性铬系催化剂主要体现为采用氧化铝和磷酸铝作为载体,或使用烷基铝作为改性剂。改性后铬系催化剂的聚合活性和氢调敏感性明显提高,由其生成聚合物的相对分子质量分布变宽,耐环境应力开裂性能改善,加工性能优异。     

乙烯聚合铬系催化剂研究进展

铬系催化剂由于活性高、制备工艺简单,且制得的聚合物产品中含有长支链组分及少量超高分子量组分,日益受到人们的关注。本文从铬系催化剂的发展历程、制备方法、聚合机理及研发现状四个角度对铬系催化剂进行了详细的阐述,并指出了今后我国铬系催化剂的研发方向。     

乙烯聚合用钛改性铬系催化剂的进展

综述了钛改性铬系催化剂的国内外研发现状、制备方法、性能以及对乙烯聚合性能的影响。与用表面浸渍法制备的钛改性铬系催化剂相比,用共凝胶法制备的钛改性铬系催化剂可以缩短诱导期,提高聚乙烯(PE)的熔体流动速率。钛改性铬系催化剂中的钛可阻止α-烯烃在PE的低相对分子质量部分插入,有效降低了含支链低相对分子质量PE的含量。随着钛的加入,低相对分子质量部分的共聚支链减少,从而可改变PE的支链分布。钛改性铬系催化剂的聚合性能明显改善,制备的聚乙烯性能优异。     

Ti,Al改性Phillips乙烯聚合催化剂的结构及性能研究

通过添加钛(Ti)、铝(Al)对Cr/SiO2 Phillips催化剂进行改性,制备出了Cr-Ti/SiO2和Cr-Ti-Al/SiO2两种改性催化剂,考察了改性催化剂的结构及催化乙烯聚合性能.结果 表明,添加Ti和Al后,催化剂表面变得粗糙,孔径变小,比表面积增大;催化活性增加,最高活性分别为55.36和82.55g...     

铬系催化乙烯配位聚合/齐聚分子模拟研究进展

针对工业中广泛应用的Phillips铬系乙烯聚合催化剂和铬系乙烯选择性齐聚催化体系,从分子模拟角度对近期相关研究进展进行综述。主要介绍了分子模拟在Phillips铬系催化剂诱导期内乙烯聚合活性中心向乙烯易位活性中心转换机理、Ti改性Phillips铬系催化剂的乙烯聚合行为、Cr(III)2-EH/PIBAO/DME体系乙烯聚合和三聚转换机理以及Cr-SNS体系去质子化对乙烯三聚活性的影响等方面的研究进展。通过计算机分子模拟和实验手段相结合,可以获得对催化反应机理更为深刻的认识,从而为新型催化剂的设计与开发提供理论指导。     

有机载体钛系催化剂在乙烯聚合中的应用

采用种子溶胀聚合制备了3种含有氰基官能团的有机聚合物载体,再负载TiCl₄制备了有机载体负载型Ziegler-Natta催化剂,研究了有机载体催化剂对乙烯聚合的影响,同时与工业上使用的无机载体型Ziegler-Natta催化剂催化乙烯聚合进行了对比。结果表明：与工业催化剂相比,有机载体催化剂活性更高,为45.0 kg/g,聚乙烯堆密度相差不大,但采用有机载体催化剂制备的聚乙烯颗粒形态较规整,且灰分含量较低,同比下降了约32.8%,聚乙烯的相对分子质量最高为4.8×10⁶,拉伸强度可达42.5 MPa,拉伸标称应变为320%,悬臂梁缺口冲击强度可达85.9 kJ/m²。     

Phillips铬系聚乙烯催化剂活性中心价态的研究进展

综述了近年来Phillips铬系聚乙烯催化剂活性中心价态的研究进展,总结了关于各种不同活性中心价态的研究结果与理论.详细介绍了Cr(Ⅲ)活性中心价态理论、Cr(Ⅱ)活性中心价态理论,并概述了其他价态的理论,如Cr(V),Cr(Ⅳ)和Cr(Ⅰ)等.     

Visualization of local ethylene polymerization activity on a flat CrO x /SiO2/Si(100) model catalyst

Flat model catalysts give access to fundamental aspects of olefin polymerization over heterogeneous catalysts. They are especially suited for the investigation on the early stages of polymer film growth employing scanning probe and electron microscopy. The polymerization centers are confined to a well defined two dimensional plane that remains constant during the polymerization. Using the Phillips (CrO _x /SiO₂) catalyst as an example we demonstrate how this approach can be used do visualize the lateral distribution of polymerization activity in the initial stages of polymer growth.     

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。     

Electron microscopic characterization of Cr/silica catalyst for ethylene polymerization

Ethylene polymerization was carried out over both porous and non-porous 5 wt% Cr/silica catalysts in a slurry reactor. The polymerization was stopped at selected times to obtain samples for SEM and TEM characterization. Despite the different physical characteristics of the two silica-supported catalysts and their different behavior in the early stages of reaction, high resolution SEM micrographs (taken after runs of longer duration) revealed similar, fibrous and very porous polymer layers on both. This accessibility of the ethylene enables transport of monomer to the active sites at the very high reaction rates.     

Planar model system for olefin polymerization: the Phillips CrO x /SiO2 catalyst

A planar CrO _x /SiO₂/Si(100) model for the Phillips ethylene polymerization catalyst has been prepared by spincoat impregnation from an aqueous solution of CrO₃. The model catalyst polymerizes ethylene from the gas phase at 160°C with a constant activity and forms a 400 nm thick layer of polyethylene in 1 h. The superior definition of the polymer films produced on this catalyst and the control over the distribution of active sites on its flat surface make this model catalyst an ideal substrate for kinetic studies on catalytic polymerization and for morphologic studies of the polymer product by scanning force microscopy. At extremely low catalyst loading we observe isolated polymer islands formed on single chromium sites. The work also opens attractive opportunities for future studies of nascent morphology of catalytically formed polymers. This revised version was published online in June 2006 with corrections to the Cover Date.     

乙烯聚合用有机铬系催化剂研究进展

综述了乙烯聚合用有机硅烷铬酸酯催化剂的结构、制备方法、聚合机理、所制备树脂产品特性以及国内外研究现状,指出了有机硅烷铬酸酯催化剂与钛系催化剂和Phillips型氧化铬催化剂的区别及其独有的特性。建议深入研究有机铬系催化剂的聚合机理、加大研发投入、加快有机铬系新产品的开发。     

浆液法高效催化剂的乙烯聚合行为

考察了浆液法聚乙烯高效催化剂在总压0．7MPa、氢气分压0．18MPa下的乙烯聚合行为，表明催化剂活性中心失活符合一级规律，Al/Ti的影响可用Langmiur-Hinshelwood吸附竞争模型来描述；温度在70－90℃条件下，利用Arrhenius方程计算出了催化剂聚合反应的表现活化能为0．11kJ/mol。     

A new iron‐based catalyst for ethylene polymerization

A new iron‐based catalyst, 2,6‐bis[(1‐naphthanylimino)ethyl]pyridine iron(II) chloride I, has been successfully synthesized and characterized. Ethylene was polymerized by I/methylaluminoxane to give branched, low‐density polymers with good activity. The result shows that the new diimino ligand has improved the characteristics of the resulting polyethylene. © 2000 Society of Chemical Industry     

铬钒双金属催化剂乙烯聚合反应动力学模型化

双金属催化剂可催化乙烯聚合在单个反应器内制备双峰聚乙烯。考察了新型Cr-iV双金属催化剂及相应的单金属S-2和iV催化剂在不同实验条件下的乙烯均聚反应动力学。通过对Cr-iV催化剂聚合产物分子量分布曲线的解析发现铬钒活性中心之间存在相互作用,铬中心活性受到抑制,钒中心活性得到增强;聚合温度基本不改变铬钒活性中心生成的聚合物的质量分数。采用简化的单中心乙烯均聚动力学模型分别描述铬钒双活性中心的动力学行为,结合双金属催化剂的聚合实验结果确定了各个活性中心的动力学参数。相比单金属催化剂,Cr-iV催化剂中铬活性中心链增长速率常数降低,说明其聚合活性降低;而钒活性中心链失活速率常数减小,稳定性增强,活性提高。     

Probing the early stages of polymerization of ethylene on a model chromium/silica catalyst by Fourier transform infrared spectroscopy

The nature of the interaction of monomer, and the early stages of growth of oligomers of ethylene on a rather more uniform surface of Cr/SiO₂ catalyst than hitherto studied has been investigated by differenceFTIR spectroscopy using C₂D₄ and C₂H₄ as reactants both with and without subsequent treatment of the catalyst with CO andTHF. The active catalyst was prepared by reaction of vapour phase CrO₂Cl₂ with the vicinal hydroxyls of the silica surface. Three distinct kinds of methylene groups were detected. Arguments are given for assigning the peaks at 2935 and 2860 cm^–1 to CH₂ groups directly bound to the active site and those at 2920 and 2850 to CH₂s in the growing chain well removed from the Cr. The peaks at 2160 and 2165 cm^–1 are attributed to CD₂ groups hydrogen bonded to surface hydroxyls.