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-i V双金属催化剂及相应的单金属S-2和i V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-i V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-i V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。     

铬/钒双金属催化剂催化乙烯气相聚合

在实验室小试气相聚合釜中对铬/钒双金属催化剂进行乙烯聚合评价,考察了不同聚合温度和压力时催化剂的性能,研究了不同条件下催化剂的动力学行为,并将其聚合动力学曲线与用工业铬系催化剂的进行了比较。结果表明:随着聚合温度升高,用铬/钒双金属催化剂制备的聚乙烯的相对分子质量减小,熔体流动速率增大,在所研究聚合温度范围内铬/钒双金属催化剂对温度更敏感;随着聚合压力增大,催化剂活性显著提高,聚乙烯相对分子质量增加;聚合动力学曲线与铬系催化剂不同,聚合反应速率先增大再降低最后逐渐达到平稳。     

(NH_4)_2SO_4改性Cr/V双金属催化剂的制备及乙烯聚合研究

在Phillips催化剂基础上开发出CrOx-VOx/SiO_2双中心催化剂,并用(NH_4)_2SO_4对其进行改性,考察了(NH_4)_2SO_4的浸渍方式、浸渍量和催化剂焙烧温度对乙烯聚合行为和产物结构与性能的影响。结果表明,(NH_4)_2SO_4改性的铬钒双金属催化剂的乙烯聚合活性得到提高,且随(NH_4)_2SO_4负载量的增加,活性呈现先增加后降低的趋势。采用共浸渍制备的催化剂的乙烯聚合活性大于分布浸渍法。(NH_4)_2SO_4对V活性组分有促进作用,使改性催化剂的均聚产物分子质量增加,加入1-己烯共聚单体后,分子质量进一步增加。     

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。     

宽或双峰分子量分布HDPE的研制Ⅰ.双金属复合催化剂的制备及其催化乙烯聚合反应动力学

将Cp2ZrCl2以一定方式负载于BCH催化剂上制备出了双金属复合催化剂,研究了BCH/Cp2ZrCl2对载锆量的影响以及负载温度对双金属复合催化剂催化性能的影响,并用X射线光电子能谱法证实了茂金属催化剂确已载到了BCH催化剂上.催化乙烯聚合的动力学研究表明,双金属复合催化剂的动力学曲线与BCH催化剂一样均属衰减型;由于双金属中心的存在,其动力学曲线出现了2个峰值.     

烷基铝预还原铬钒双中心催化剂的制备及其催化乙烯聚合北大核心

在Phillips无机铬系催化剂基础上开发了新型铬钒双中心聚乙烯催化剂,分别选用三乙基铝(TEAL)和三异丁基铝(i-Bu_3Al)作为助催化剂以及预还原剂对该双中心催化剂的乙烯聚合活性及产品结构性能进行了研究。结果表明:以TEAL与i-Bu_3Al分别作为预还原剂得到的两种催化剂在聚合过程中助催化剂的用量极大降低;使用相同助催化剂时,上述两种催化剂聚合活性的高低和变化趋势基本一致,得到的产品相对分子质量及其分布基本相同,说明TEAL和i-Bu_3Al的预还原效果相近;采用预还原催化剂制备的共聚产物的1-己烯插入率显著提高,降低了1-己烯的用量。     

宽或双峰分子量分布HDPE的研制：Ⅰ双金属复合催化剂的制备？…

将Ｃｐ２ＺｒＣｌ２以一定方式负载于ＢＣＨ催化剂上制备了双金属复合催化剂,了ＢＣＨ／Ｃｐ２ＺｒＣｌ２对载锆量的影响以及负载温度对双金属复合催化剂催化性能的影响,并用Ｘ射线光电子能谱法证实了藏金属催化剂确已载到了ＢＣＨ催化剂上。催化乙烯聚合的动力学研究表明,双金属复合催化剂的动力学曲线与ＢＣＨ催化剂一样均属衰减型;由于双金属中心的存在,其动力学曲线出现了２个峰值。     

烷基铝预还原铬钒双中心催化剂的制备及其催化乙烯聚合

在Phillips无机铬系催化剂基础上开发了新型铬钒双中心聚乙烯催化剂,分别选用三乙基铝(TEAL)和三异丁基铝(i-Bu_3Al)作为助催化剂以及预还原剂对该双中心催化剂的乙烯聚合活性及产品结构性能进行了研究。结果表明:以TEAL与i-Bu_3Al分别作为预还原剂得到的两种催化剂在聚合过程中助催化剂的用量极大降低;使用相同助催化剂时,上述两种催化剂聚合活性的高低和变化趋势基本一致,得到的产品相对分子质量及其分布基本相同,说明TEAL和i-Bu_3Al的预还原效果相近;采用预还原催化剂制备的共聚产物的1-己烯插入率显著提高,降低了1-己烯的用量。     

单活性中心乙烯聚合催化剂的研究进展

单活性中心乙烯聚合催化剂是近年来国内外研究的热点,也是开发聚乙烯新产品的重要手段。本文综述了近年来单活性中心催化剂用于制备功能性聚乙烯材料的研究进展,包括茂金属催化剂、非茂金属催化剂的开发应用。通过对单活性中心催化剂结构的调控,可以得到分子量及分子量分布、分子结构、构象等精确可控的功能性乙烯共聚物,或具有特殊性能的聚乙烯产品。     

单活性中心催化剂及其聚合工艺进展

综述了十几年来用于烯烃聚合的单活性中心均相催化剂的研究开发状况,主要包括茂金属催化剂、后过渡金属络合物催化剂以及其它的新型催化剂体系。讨论了新一代单活性中心催化剂对传统聚合工艺的冲击和发展。     

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。     

Comonomer effects in copolymerization of ethylene and 1‐hexene with MgCl2‐supported Ziegler‐Natta catalysts: New evidences from active center concentration and molecular weight distribution

In this article, comonomer effects in copolymerization of ethylene and 1‐hexene with four MgCl₂‐supported Ziegler‐Natta catalysts using either ethylene or 1‐hexene as the main monomer were investigated. It was found that no matter which monomer was used as the main monomer, the polymerization activity was significantly enhanced by introducing small amount of comonomer. In copolymerization with ethylene as the main monomer, the strength of comonomer effects was much stronger in active centers producing low‐molecular‐weight polymer than those producing high‐molecular‐weight polymer. In copolymerization with 1‐hexene as the main monomer, the number of active centers ([C*]/[Ti]) was determined, and the propagation rate constants (k_p) were calculated. Deconvolution of the polymer molecular weight distribution into Flory components were made to study the active center distribution. Introduction of small amount of ethylene caused marked increase in the number of active centers and decrease in average chain propagation rate constant. Introducing internal electron donor in the catalyst enhanced not only the number of active centers but also the chain propagation rate constant. In copolymerization of 1‐hexene with small amount of ethylene, the internal donor weakened the comonomer effects to some extent and changed the distribution of comonomer effects among different types of active centers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41264.     

Ethylene polymerization over supported titanium‐magnesium catalysts: Effect of polymerization parameters on the molecular weight distribution of polyethylene

The data on the effects of polymerization duration, cocatalyst, and monomer concentrations upon ethylene polymerization in the absence of hydrogen, and the effect of an additional chain transfer agent (hydrogen) on the molecular weight (MW), molecular weight distribution (MWD), and content of vinyl terminal groups for polyethylene (PE) produced over the supported titanium‐magnesium catalyst (TMC) are obtained. The effects of these parameters on nonuniformity of active sites for different chain transfer reactions are analyzed by deconvolution of the experimental MWD curves into Flory components. It has been shown that the polymer MW grows, the MWD becomes narrower and the content of vinyl terminal groups in PE increases with increasing polymerization duration. It is assumed to occur due to the reduction of the rate of chain transfer with AlEt₃ with increasing polymerization duration. The polydispersity of PE is found to rise with increasing AlEt₃ concentration and decreasing monomer concentration due to the emergence of additional low molecular weight Flory components. The ratios of the individual rate constants of chain transfer with AlEt₃, monomer and hydrogen to the propagation rate constant have been calculated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Copolymerization of ethylene with α-olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

The data on the effect of comonomer (propylene and 1-hexene) on molecular weight (M_w), molecular weight distribution (MWD), and content of terminal double bonds were obtained for ethylene/α-olefin copolymers produced over a supported titanium–magnesium catalyst (TMC) upon polymerization in the absence of hydrogen. The experimental data on the effect of comonomer concentration on M_w of polymers were used to calculate the ratios between the effective rate constants of chain transfer with monomer and the propagation rate constant. It was shown that the effective rate constant of chain transfer with monomers increases in the row of monomers: ethylene < 1-hexene < propylene. Meanwhile, the data on the effect of copolymers on content of terminal double bonds of various types demonstrate that different reactions of chain transfer with comonomer may simultaneously occur during copolymerization. It results in simultaneous formation of terminal vinylidene and trans-vinylene bonds. Therefore, the calculated rate constants of chain transfer with comonomer are complex values, which include the rate constants of chain transfer with comonomer occurring via different mechanisms. The data on MWD, short chain branching (SCB) and terminal double bonds content of different types were obtained by molecular weight fractionation of copolymers followed by the analysis of narrow fractions. The analysis of the data on MWDs of SCB and terminal double bonds shows that active sites of the TMC are considerably heterogeneous with respect to the rates of different chain transfer reactions with monomers. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergy of ruthenium and cobalt in SiO2-supported catalysts on ethylene hydroformylation

Dynamic hydroformylation of ethylene at atmospheric pressure and 150°C has been studied in a fixed bed reactor over ruthenium- and cobalt-containing SiO₂-supported catalysts (1% Ru loading). Any combination of ruthenium and cobalt precursors leads to significant improvement of hydroformylation activity with respect to those of monometallic catalysts. The optimal atomic ratio of Co:Ru is estimated to be 3:1 for ideal catalytic activity. A catalyst derived from Ru₃(CO)₁₂ and Co₂(CO)₈ is most active. A catalyst derived from metal carbonyls is generally more active than a catalyst prepared from metal salts. Metal chlorides retard the preparation of active catalysts in most cases. The catalysts studied exhibit fairly good catalytic stability. The determined rate enhancement of ethylene hydroformylation suggests a synergy of ruthenium and cobalt, which is understood as catalysis by bimetallic particles or ruthenium and cobalt monometallic particles in intimate contact. The synergy causes high ethylene hydrogenation activity while giving enhanced ethylene hydroformylation activity. Meanwhile, the potential of the ruthenium-based catalysts is evaluated from both catalytic performances and cost by comparison with the corresponding rhodium-based ones.     

Influence of the nature of monomers on the activity of supported titanium catalysts in the α-olefin polymerization

Summary Ethylene and propylene co-polymerization and sequential polymerization with high activity supported titanium catalysts were studied. Specific rate of homopolymerization and copolymerization constants for ethylene and propylene were determined by using the derived values of the solubility constants for monomers in nascent polymers. The reason of the increased rate of co-polymerization upon enriching the monomers mixture with propylene, the effect of activation of ethylene polymerization upon preliminary polymerization of propylene may be in the increasing number of active sites due to enlarged content of amorphous phase in the nascent polymer product.     

A kinetic study of novel bimetallic titanocene catalyst for syndiospecific styrene polymerization

A kinetic study of a syndiospecific polymerization was performed with two kinds of catalysts: Cp*Ti(O(C₆H₄)CMe₂(C₆H₄)O)TiCp* [bimetallic system] and Cp*Ti(OMe)₃ [monometallic system]. The purpose of this study was to determine the reasons behind the high activity of a bimetallic catalyst system. The active site structures of the two kinds of catalysts appears to be similar to the cationic Ti [III] species having η⁵‐pentamethylcyclopentadienyl ligand, while the rate of the activation process of the bimetallic catalyst was found to be higher than that of the monometallic catalyst. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Copolymerization of ethylene and cyclopentene with the Phillips CrOx/SiO2 catalyst in the presence of an aluminum alkyl cocatalyst

The Phillips CrO_x/SiO₂ catalyst is an important industrial catalyst for ethylene polymerization. However, understanding of the state of active sites and chain propagation mechanisms concerning the Phillips catalyst is still waiting for conclusive evidence. In this work, the Phillips CrO_x/SiO₂ catalyst, having been calcined, was used for investigating the copolymerization of ethylene and cyclopentene in the presence of triethylaluminum as a cocatalyst for the first time. The microstructures of the polymers were investigated with ¹³C‐NMR and gel permeation chromatography methods. Because of the absence of internal double bond (C?C) in the copolymer main chain, the ring‐opening metathesis polymerization of cyclopentene was excluded during the copolymerization stage of ethylene and cyclopentene. Also, the 1,2‐insertion and 1,3‐insertion of cyclopentene into the polyethylene main chain were confirmed. This evidence strongly implies that Cr?C species may not be the active sites for chain propagation; instead, the Cr? C active site model under the Cossee–Arlman chain propagation mechanism may be responsible for the chain propagation during the normal polymerization period. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hydrogen effect on the molecular weight distribution of polymers obtained by polymerization of ethylene and α-olefins over supported titanium-magnesium catalysts

Comparative data on the molecular weight distribution of polymers obtained by polymerization of ethylene, propylene and 1-hexene, and copolymerization of ethylene with α-olefins over the titanium-magnesium catalysts (TMC) in the absence and presence of hydrogen are presented. In contrast to the ethylene polymerization, in the cases of propylene and 1-hexene polymerization and copolymerization of ethylene with α-olefins, the hydrogen addition is characterized by noticeable narrowing of the molecular weight distribution (MWD) due to lower contribution of the MWD component with high molecular weight. This result is an evidence of the increased reactivity of TMC active sites producing high molecular weight poly-α-olefins and copolymers of ethylene with α-olefins in the chain transfer reaction with hydrogen. It is suggested that the increased reactivity of these sites in the transfer reaction with hydrogen appears after the 2,1-addition of α-olefin to the growing polymer chain.     

纳米钯金铁三金属催化剂的制备及其对三氯乙烯的降解

在乙醇-水体系中利用硼氢化物液相还原法合成纳米铁颗粒,通过化学沉淀法将钯金粒子负载于纳米铁表面,得到纳米钯金铁(Pd-Au@Fe)三金属催化剂复合材料,采用TEM, EDS和XPS对其进行表征. 结果表明,与纳米单金属Fe0及双金属Pd@Fe相比,三金属催化剂对三氯乙烯(TCE)具有更高的降解能力. 保持催化剂加量1.4 g/L, Pd/Fe为0.35%(w), Au/Fe为1.0%(w)时,其降解15 mg/L TCE的速度最快,5 min时去除率为88.21%,表观速率常数为0.311 min-1,是相同Pd含量下Pd@Fe双金属催化剂的3.6倍. 随降解反应持续,Pd-Au@Fe的乙烯乙烷生成率及乙烯加氢转换乙烷速率均远高于双金属Pd@Fe.