Synthesizing UHMWPE Using Ziegler-Natta Catalyst System of MgCl2(ethoxide type)/ TiCl4/tri-isobutylaluminum

Summery: A Ziegler-Natta catalyst of MgCl₂ (ethoxide type)/TiCl₄ has been synthesized. In order to obtain ultra high molecular weight polyethylene (UHMWPE) tri-isobutylaluminum which is less active to chain transfer was used as cocatalyst. Slurry polymerization was carried out for the polymerization of ethylene while, dilute solution viscometry was performed for the viscosity average molecular weight (Mv) measurement. The effect of [Al]/[Ti] molar ratio, temperature, monomer pressure and polymerization time on the Mv and productivity of the catalyst have been investigated. The results showed increasing [Al]/[Ti] ratio in the range of 78–117, decreased the Mv of the obtained polymer from 7.8 × 10⁶ to 3.7 × 10⁶ however, further increase of the ratio, resulted in decreased of by much slower rate up to [Al]/[Ti] = 588. The higher pressure in the range of 1–7 bars showed the higher the Mv of the polymer obtained, while increasing temperature in the range of 50 to 90 °C decreased the Mv from 9.3 × 10⁶ to 3.7 × 10⁶. The Mv rapidly increase with polymerization time in the first 15 minutes of the reaction, this increase was slowly up to the end of the reaction (120 min). Increasing [Al]/[Ti] ratio raised productivity of the catalyst in the range studied. Rising reaction temperature from 50 to 75 °C increased the productivity of the catalyst however, further increase in the temperature up to the 90 °C decreased activity of the catalyst. Monomer pressure in the range 1 to 7 bars yields higher productivity of the catalyst. Also by varying polymerization conditions synthesizing of UHMWPE with Mv in the range of 3 × 10⁶ to 9 × 10⁶ was feasible.     

Experimental and Computational Approaches on the Isospecific Role of Monoester-Type Internal Electron Donor for TiCl4/MgCl2 Ziegler-Natta Catalysts

In this work, a combination of experimental and computational approaches on the isospecific role of monoester-type internal electron donors (ED) such as phenylpropionate (PhP), ethylheptanoate (EH), methylbenzoate (MB), ethylbenzoate (EB) for TiCl₄/ED/MgCl₂ Ziegler-Natta catalysts had been performed. The propylene polymerization results revealed that the isospecificity of catalysts increases in the following order: PhP < EH < MB < EB. The subsequent molecular modeling on the electronic properties of the donors and two kinds of cluster model catalysts: TiCl₄/ED/MgCl₂ and TiCl₄/ED/(MgCl₂)₄ based on density functional theory (DFT) method was carried out. Two kinds of ED coordination on MgCl₂ clusters through either O or  O within the monoester-type ED had been disclosed. A perfect correlation between the dipole moment of ED, the coordination bond length of O … Mg, the competitive coordination from  O with Mg ion and the isospecificity of the catalysts had been established.     

A study of polyethylene-gr-2-tert-butyl amino methacrylate-supported TiCl4 catalyst for ethylene polymerization

The use of a polyethylene-based copolymer with dual functional groups (polyethylene-gr-2-tert-butyl amino ethyl methacrylate) as the support for TiCl₄ catalyst in ethylene polymerization was studied. Different methods for treating the support were examined and treatment with BuMgCl was found to be the most effective. With the BuMgCl-modified support, a 12-run Plackett-Burman design was used to screen 11 factors in catalyst preparation. Statistical analysis of the results from this design identified significant factors with the amount of BuMgCl singled out to be the most important one for the four response variables of interest, Mg loading, Ti loading, catalyst activity per gram catalyst, and catalyst activity per gram Ti. © 1996 John Wiley & Sons, Inc.     

Hexene-1 polymerization by homogeneous zirconocene and heterogeneous-supported TiCl3 catalysts

MgCl₂-supported TiCl₃ catalysts, with and/or without electron donor modifier (internal B_i or external B_e), were compared with rac-ethylenebis(indenyl)zirconium dichloride ( 1 ) activated with either MAO or the cation forming agent, triphenyl carbenium tetrakis(pentafluorophenyl)borate ( 2 ), with triethylalumium (TEA). The activities of the heterogeneous catalysts depend on the presence or absence of the Lewis base, were relatively insensitive to the temperature of polymerization, and produce poly(hexene) with molecular weights up to 10⁶. The 1 /MAO catalyst has about five times higher activity at 50°C but is almost inactive at ?30°C; the overall activation energy is 12.4 kcal mol^?1. In contrast, the activity for hexene polymerization by the 1/2 /TEA catalyst is actually slightly greater at lower temperature. The MW's of poly(hexene) obtained with the zirconocenium catalysts are only in the tens of thousands because of rapid β-hydride elimination by the electrophilic cationic Zr center. © 1993 John Wiley & Sons, Inc.     

The discovery and progress of MgCl2‐supported TiCl4 catalysts

Polyolefins represented by polyethylene (PE) and polypropylene (PP) are indispensable materials in our daily lives. TiCl₃ catalysts, established by Ziegler and Natta in the 1950s, led to the births of the polyolefin industries. However, the activities and stereospecificities of the TiCl₃ catalysts were so low that steps for removing catalyst residues and low stereoregular PP were needed in the production of PE and PP. Our discovery of MgCl₂‐supported TiCl₄ catalysts led to more than 100 times higher activities and extremely high stereospecificities, which enabled us to dispense with the steps for the removals, meaning the process innovation. Furthermore, they narrowed the molecular weight and composition distributions of PE and PP, enabling us to control the polymer structures precisely and create such new products as very low density PE or heat‐sealable film at low temperature. The typical example of the product innovations by the combination of the high stereospecificity and the narrowed composition distribution is high‐performance impact copolymer used for an automobile bumper that used to be made of metal. These process and product innovations established these polyolefin industries. The latest MgCl₂‐supported TiCl₄ catalyst is very close to perfect control of isotactic PP structure and is expected to bring about further innovations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1–8, 2004     

Modification of the(SiO_2/MgO/MgCl_2)·TiCl_x Ziegler-Natta Polyethylene Catalysts Using the Third Metal Elements

Various(SiO_2/MgO/MgCl_2)·Ti Clx Ziegler-Natta catalysts modified by the third metal elements were synthesized by the co-impregnation of water-soluble magnesium and the third metal salts. Several key factors including the electronegativity of the third metal elements, catalyst performances in ethylene homo-polymerization, ethylene/1-hexene copolymerization and hydrogen response were systematically investigated. Both the catalyst performance and the polymer properties are influenced by the introduction of the third metal elements. Compared with the unmodified(SiO_2/MgO/MgCl_2)·Ti Clx Ziegler-Natta catalyst, activity and 1-hexene incorporation are enhanced by the introduction of zirconium, vanadium, aluminum and chromium, while deteriorated by the addition of ferrum, nickel, molybdenum and tungsten. Correlations of the catalyst activities and 1-hexene incorporation ability with the electronegativity of the third metal elements are discovered. It is found that the lower electronegativity of the third metal elements leads to the catalyst with higher activity and higher α-olefin co-polymerization ability. The polyethylene produced by a nickel modified catalyst showed broad molecular weight distribution(MWD) and the lowest average molecular weight(MW), while by using a ferrum modified catalyst, the resulting polyethylene had the highest MW, reaching the ultra-high MW area. Vanadium and chromium modified catalysts demonstrated the best hydrogen response.     

共轭二烯烃的Ziegler─Natta催化聚合

共轭二烯烃的聚合是配位阴离子聚合，双金属配合物是聚合的活性中心，控制单体的构象是控制聚合物结构的关键。单体在低值配位场稳定化能（ＬＦＳＥ）过渡金属离子，如Ｃｏ~（２＋）、Ｔｉ~（３＋）上螯合，螯合单体具有顺式构象，所得聚合物具有顺１，４结构；在中等ＬＦＳＥ的过渡金属离子，如Ｖ~（３＋）、Ｃｒ~（３＋）上配位，配位单体具有反式构象，所得聚合物具有反１，４结构或是１，２聚合物；高ＬＦＳＥ值过渡金属离子不易控制活性价态，双金属配合物不够稳定，所得聚合物分子量常较低，结构规整性也常不够理想。     

MgCl_2负载TiCl_4催化剂中内给电子体对活性组分钛的影响

应用XPSI、R等表征手段研究了以MgCl2为载体,苯甲酸酯、邻苯二甲酸酯以及1,3-二醚为内给电子体的Ziegler_Natta(Z-N)催化剂中内给电子体对活性组分Ti的作用.实验结果表明,不同内给电子体Z-N催化剂中Ti的氧化状态是不同的,给电子体不与Ti直接发生作用,而是通过MgCl2为媒介向Ti发生电荷转移,造成Ti周围电子云密度增大,Ti的氧化状态降低,表现为Ti的结合能下降.     

A comparative study of 2,2,6,6-tetramethylpiperidine (TMPiP) and ethyl benzoate on (110) β-MgCl2

A semiempirical theoretical method (ICONC) which includes core-core repulsion to the energy terms was used to characterize the 2,2,6,6-tetramethylpiperidine (TMPiP)/MgCl₂ system and the ethyl benzoate (EB)/MgCl₂ system by modeling TMPiP and EB adsorption on the (110) face of β-MgCl₂.     

A comparative study of 2,2,6,6-tetramethylpiperidine (TMPiP) and ethyl benzoate on (100) β-MgCl2

An Extended Hückel Method (ICONC) which includes core-core repulsion to the energy terms was used to characterize the 2,2,6,6-tetramethylpiperidine (TMPiP)/MgCl₂ system and the ethyl benzoate (EB)/MgCl₂ system by modeling TMPiP and EB adsorption on the (100) face of β-MgCl₂.     

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。     

Development of novel MgCl2 supported catalyst with trivalent titanocene complex of CP2TiCl2AlCl2 for propylene polymerization

Three kinds of MgCl₂‐supported trivalent titanocene catalyst (Cat. 1: Cp₂TiCl₂AlCl₂/MgCl₂, Cat. 2: CpCp*TiCl/MgCl₂, Cat. 3: Cp₂TiCl/MgCl₂) were prepared and tested for propylene polymerization. It was found that Cat. 1, combined with ordinary alkylaluminum as cocatalyst, produced PP containing 31.8 wt % of isotactic PP in fairly good yield. On the other hand, Cats. 2 and 3 hardly showed any activity. The effects of diisopropyldimethoxysilane (DIPDMS) on isospecificity of the Cat. 1 also were investigated. The isotactic index (I.I.) of PP was improved drastically by the addition of DIPDMS as external donor and reached the value as high as 98.4%, even in the absence of any internal donors. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3355–3359, 2000     

石墨烯/二氯化镁负载钛系齐格勒-纳塔催化剂制备及其乙烯聚合性能

石墨烯自2004年发现以来,由于其独一无二的优异性迅速成为科学家们的研究热点.由于石墨烯具有极其优异的电学、力学和热学等性能,因此被广泛应用于高性能聚合物基复合材料的制备.众所周知,纳米填料在聚合物中的分散状态以及与基体间的界面作用是构筑高性能聚合物纳米复合材料的关键因素.由于石墨烯极易团聚,难以通过传统的熔融共混法制备均匀分散的石墨烯增强-聚烯烃纳米复合材料.另一方面,聚烯烃通常需要在较高温度下才能溶于部分有毒溶剂(如:三氯苯和二甲苯等),因此溶液共混法也不适用于聚烯烃-石墨烯纳米复合材料的制备.有鉴于此,本文开发了一种共沉积法制备石墨烯/二氯化镁负载钛系齐格勒-纳塔催化剂的路线.通过原位聚合直接制备出石墨烯均匀分散的聚烯烃/石墨烯纳米复合材料.考察了石墨烯的加入量对催化剂形态及其催化乙烯聚合行为的影响.当石墨烯加入量较低时,多个石墨烯片被包裹于较大的催化剂粒子中.随着石墨烯加入量的增加,催化剂趋向于在石墨烯表面聚集.继续增加石墨烯量将导致石墨烯包裹催化剂粒子,降低过渡金属钛的负载效率.通过三乙基铝活化后,所制备的催化剂具有非常高的乙烯催化活性,所生成的聚乙烯/石墨烯纳米复合材料复制了催化剂的片状结构.同时,通过对所制备的聚乙烯/石墨烯纳米复合材料进行电子显微镜和X射线衍射分析可知,石墨烯均匀分散于聚乙烯基体中,并且没有任何团聚现象发生.该复合材料的热重分析表明,仅加入非常少量的石墨烯就可以使其具有比纯聚乙烯更高的热稳定性,当石墨烯加入量为0.66 wt%时,其5 wt%热分解温度较纯聚乙烯升高了54°C.同时,所制备聚乙烯/石墨烯纳米复合材料具有更优异的机械性能.因此,本研究提供了一个简单高效的高性能聚烯烃/石墨烯纳米复合材料的制备方法.     

Adsorption of TiCl4 and electron donor on defective MgCl2 surfaces and propylene polymerization over Ziegler-Natta catalyst: A DFT study

The formations of defective MgCl₂ surfaces, and subsequent adsorption of Ti species and electron donor, as well as propylene polymerization over the Ziegler-Natta catalyst have been investigated using density functional theory (DFT) method. Twelve possible support models of regular and defective MgCl₂ (110) and (100) surfaces were built. The individual adsorptions of titanium chlorides as mononuclear or dinuclear, and ethyl benzoate (EB) as electron donor, on these models were evaluated. The analysis of energies presented the cases of EB adsorption were generally more stable than titanium chlorides on both surfaces. Thus, EB as internal electron donor mainly prevented TiCl₄ from coordinating on the MgCl₂ surfaces where mostly non-stereospecific active sites could be formed. Exceptionally, A5 the site model with terminal Cl-vacancy on the MgCl₂ support, presented stronger adsorption of TiCl₄ than that of EB on (110) surface. Since the TiCl₄ and ethyl benzoate (EB) would compete to adsorb on the support surface, it seems reasonable to assume that TiCl₄ might predominately occupy this site, which can act as the most plausible active site for propylene polymerization. The first insertion of propylene monomer into the A5 active site model showed that it exhibited good regioselectivity but poor stereospecificity in the absence of electron donor.     

丙烯聚合用TiCl_4/MgCl_2催化剂的研究——聚合温度和烷基铝的影响

研究了不同助催化剂和不同聚合温度对催化剂TiCl4/MgCl2/9,9-双(甲氧基甲基)芴(BMMF)丙烯聚合性能的影响.研究结果发现该催化剂在高温(100℃)聚合时,采用还原能力和络合能力较弱的烷基铝(Hex3Al)为助催化剂可以得到高的立构选择性(97%)和高活性.100℃聚合时不同的助催化剂对催化剂得到的聚丙烯结构有重要影响.助催化剂为Me3Al聚合得到的中等等规聚丙烯含量比其他烷基铝高.助催化剂为Et3Al聚合得到聚丙烯链结构中含有少量乙烯共聚单元;而助催化剂为Me3Al,iBu3Al和Hex3Al聚合得到聚丙烯链结构中没有发现共聚单元.     

MgCl2/R'nAl(OR)3-n: an excellent activator/support for transition-metal complexes for olefin polymerization

A new and effective method for the activation, and simultaneously, immobilization of bis(phenoxyimine) early-transition-metal complexes for olefin polymerization (known as FI catalysts), which makes use of MgCl(2)/R'(n)Al(OR)(3-n) as an activator/support, has been developed. Ti-, Zr-, and V-FI catalysts combined with this MgCl(2)-based compound can form highly active MgCl(2)-supported single-site catalysts capable of demonstrating superior catalytic properties, compared to the corresponding homogeneous methylaluminoxane- (Ti- and Zr-FI catalysts) or alkylaluminum-activation systems (V-FI catalysts), in terms of their catalytic activity, molecular weight, stereoselectivity, and comonomer incorporation. Additionally, these new catalysts can produce polymers of significant morphology with high efficiency. Notably, the MgCl(2)-based compounds can also effectively activate and immobilize the early-to-late transition-metal complexes that have emerged recently. Thus, the application of MgCl(2)-based compounds as activators/supports for transition-metal complexes for olefin polymerization provides a conceptually new strategy for the development of methylaluminoxane- and borate-free, high-performance, single-site catalysts capable of controlling polymer morphology.     

Copolymerization of ethylene and 1-hexene with TiCl4/MgCl2 catalysts modified by 2,6-diisopropylphenol

A supported TiCl4/MgCl2 catalyst without internal electron donor (O-cat) was prepared firstly. Then it was modified by 2,6-diisopropylphenol to make a novel modified catalyst (M-cat). These two catalysts were used to catalyze ethylene/1-hexene copolymerization and 1-hexene homopolymerization. The influence of cocatalyst and hydrogen on the catalytic behavior of these two catalysts was investigated. In ethylene/1-hexene copolymerization, the introduction of 2,6-iPr2C6H3O-groups did not deactivate the supported TiCl4/MgCl2 catalyst. Although the 1-hexene incorporation in ethylene/1-hexene copolymer prepared by M-cat was lower than that prepared by O-cat, the composition distribution of the former was narrower than that of the latter. Methylaluminoxane (MAO) was a more effective activator for M-cat than triisobutyl-aluminium (TIBA). MAO led to higher yield and more uniform chain structure. In 1-hexene homopolymerization, the presence of 2,6-iPr2C6H3O-groups lowered the propagation rate constants. Two types of active centers with a chemically bonded 2,6-iPr2C6H3O-group were proposed to explain the observed phenomena in M-cat.     

Kinetic study of gas phase olefin polymerization with a TiCl4/MgCl2 catalyst I. Effect of polymerization conditions

This study focuses on the kinetics of ethylene/propylene (homo/co) polymerization reactions using a high activity TiCl₄/MgCl₂/AlEt₃ catalyst. The reactor system is a gas phase reactor equipped with an on-line composition control scheme. As such, important kinetic data such as the instantaneous reaction rate of each monomer is readily obtained. In the investigation, experiments are performed to study the effects of comonomer composition variations, temperature variations, hydrogen concentration variations, and variations in the Al/Ti ratio. It is observed that the ethylene and propylene instantaneous reaction rates show a rather peculiar pattern with the appearance of a second peak. Our work linked the existence of this peak to the Al/Ti ratio used. A theory based on the oxidation state change is proposed. This theory is also used to explain the effects of temperature changes and hydrogen concentration changes on the system. A variety of analytical techniques are employed to study the polymer properties and evidence is provided to support the existence of polymer partial melting at relatively high reaction temperatures. The resulting diffusion limitation is believed to be partially responsible for the observed activity decrease at such elevated temperatures. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2063–2074, 1997     

Defects distribution of metallocene and MgCl2-supported Ziegler-Natta isotactic poly(propylenes) as revealed by fractionation and crystallization behaviors

The inter and intramolecular distribution of defects of poly(propylenes) of the Ziegler-Natta (ZN) and metallocene (M) types, with matched molar masses and overall defect concentrations, are inferred from the crystallization and polymorphic behavior of their narrow molecular mass fractions. The fractions obtained from the M-iPP display a range in molecular masses but the same concentration of defects and provide direct evidence of the uniform intermolecular defect distribution and the “single site” nature of the catalyst. The stereodefects of the ZN-iPP fractions are more concentrated in the low molecular mass fractions, corroborating a broad interchain distribution of the nonisotactic content. In addition, the invariance of the linear growth rates among the ZN fractions and very low contents of the gamma polymorph, developed even by the most defected ZN fraction, are consistent with a stereo blocky intramolecular distribution of defects in the ZN-iPP molecules. In contrast to the linear growth rates, which are sensitive to the defect microstructure, the overall crystallization rates correlate with nucleation density and not necessarily with the iPP chain microstructure.     

New penta-ether as the internal donor in the MgCl2-supported Ziegler-Natta catalysts for propylene polymerization

The penta-ether compound was synthesized by the reaction of di(trimethylolpropane) with sodium hydride as the strong base and methyl iodide as the alkyl halide. This compound was characterized by NMR, FTIR, and GC techniques. The MgCl₂-supported titanium catalysts were incorporated with varying amounts of penta-ether compound as the internal donor and also the catalysts without the internal donor were synthesized. The synthesized catalysts and the conventional Ziegler- Natta catalyst were characterized. The titanium contents were determined by spectrophotometry, magnesium by complexometric titration and chloride by argentometric titration. The effects of the new internal donor on propylene polymerization with the prepared MgCl₂-supported Ziegler-Natta catalysts were investigated and then these results were compared to the results obtained using the conventional diisobutyl phthalate-besed-Ziegler-Natta catalyst. The highest crystallinity degree, melting temperature, and isotacticity of polypropylene were obtained using the catalyst with a penta-ether/Mg molar ratio equal to 0.21.