烯烃聚合催化剂的研究进展

获得高性能聚烯烃材料是化学家们不断的追求。烯烃聚合催化剂的结构对其催化性能有重要影响,而聚烯烃的改性则能够改善聚合物实际应用中表面形貌、本体性能中存在的缺陷,如通过改性可增加聚合物韧性、降低聚合物表面的摩擦系数或提升表面能等。 本文系统总结了金属烯烃聚合催化剂研究进展,包括Ziegler-Natta催化剂、茂金属催化剂、非茂金属催化剂的结构及调控策略,探讨了位阻效应、双金属协同效应以及其他效应对催化效果的影响。     

A novel zirconocene/ultradispersed diamond black powder supported catalytic system for ethylene polymerization

A novel carrier of ultradispersed diamond black powder (UDDBP) was used to support metallocene catalyst. Al₂O₃ was also used as carrier in order to compare with UDDBP. Supported catalysts for ethylene polymerization were synthesized by two different reaction methods. One way was direct immobilization of the metallocene on the support, the other was adsorption of MAO onto the support followed by addition of the metallocene. Four supported catalysts Cp₂ZrCl₂/UDDBP, Cp₂ZrCl₂/Al₂O₃, Cp₂ZrCl₂/MAO/UDDBP and Cp₂ZrCl₂/Al₂O₃/MAO were obtained. The content of the zirconium in the supported catalyst was determined by UV spectroscopy. The activity of the ethylene polymerization catalyzed by supported catalyst was investigated. The influence of Al/Zr molar ratio and polymerization temperature on the activity was discussed. The polymerization rate was also observed.     

Functionalized polystyrene as a versatile support for olefin polymerization catalysts

Heterogeneous polyolefin catalysts based on metallocenium salts of weakly coordinating anions can be prepared via a series of simple reactions from lightly crosslinked chloromethylated polystyrene beads. Catalytic sites are distributed homogeneously throughout the polystyrene particles. The nonporous nature of these catalysts affords a high degree of control over the olefin uptake rate, avoiding problems of premature catalyst fragmentation that often plague high‐surface‐area heterogeneous catalysts based on highly reactive species. The choice of amine as the means of binding or templating allows catalysts based on a wide variety of metallocenes to be readily prepared by the same synthetic approach. The dative interactions between the metallocene cation and the amine functionality of the support material are sufficient to prevent extraction under polymerization conditions to yield excellent particle morphology of the polyolefin product, but they are not so strong as to affect the nature of the polyolefin produced. The polymer‐supported catalysts have been used effectively for the polymerization of ethylene and polypropylene. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2979–2992, 2000     

New organic supports for metallocene catalysts applied in olefin polymerizations

Nano-sized latex particles as organic supports for metallocenes applied in olefin polymerizations are introduced. The particles are functionalized with nucleophilic surfaces such as polyethylenoxide (PEO), polypropyleneoxide (PPO) or pyridine units allowing an immobilization of the metallocene catalysts via a non-covalent immobilization process. The latices are obtained by emulsion or miniemulsion polymerization with styrene, divinylbenzene as the crosslinker, and either PEO or PPO functionalized styrene or 4-vinylpyridine for surface functionalization. The supported catalysts, e.g. [Me₂Si(2MeBenzInd)₂ZrCl₂/MAO] on PPO containing latices or Cp₂ZrMe₂/([Ph₃C][B(C₆F₅)₄]) on pyridine functionalized materials were tested in ethylene polymerizations. Remarkably, high activities and excellent product morphologies were obtained. The influence of the degree of surface functionalization on activity and productivity was investigated. Furthermore, the fragmentation of the catalyst was studied by electron microscopy using bismuth-labeled latex particles or by fluorescence and confocal fluorescence microscopy using dye-labeled supports. Finally, a self-immobilizing catalyst/monomer system is presented. It is demonstrated that by using PEO-functionalized olefins, the metallocenes were immobilized on the monomers. Subjecting these mixtures to an ethylene copolymerization, again high activities and productivities as well as polyolefin beads with high bulk densities are observed, indicating that an extra supporting process for controlling the product size and shape of the polyolefins is not necessary for these monomers.     

Post‐Metallocenes in the Industrial Production of Polyolefins

Research on “post‐metallocene” polymerization catalysis ranges methodologically from fundamental mechanistic studies of polymerization reactions over catalyst design to material properties of the polyolefins prepared. A common goal of these studies is the creation of practically useful new polyolefin materials or polymerization processes. This Review gives a comprehensive overview of post‐metallocene polymerization catalysts that have been put into practice. The decisive properties for this success of a given catalyst structure are delineated.     

The particle‐forming process of SiO2‐supported metallocene catalysts

Homogeneous metallocene catalysts for the polyolefin production show compared with conventional Ziegler systems remarkable advantages, like the possibilities to regulate the microstructure leading to optimized polymer properties. However, for industrial application it is necessary to immobilize the metallocenes on a heterogeneous support. The parameters which now influence polymerization kinetics, polymer growth, polymer morphology, the decisive particle fragmentation are demonstrated and summarized in a physical and mathematical model.     

Development of studies devoted to design of polymer-immobilized catalysts

The state of the art in the field of designing metal-complex catalysts for olefin polymerization immobilized on polymer supports is analyzed. The types of polymers used for binding transition-metal compounds and organoaluminum components and the topochemistry of their distribution and transformations in the course of catalyzed reactions are considered. Polymer-immobilized bimetallic catalysts show promise in the catalysis of the polymerization process in which the key role of a macroligand is to unite active centers of various kinds. It has been shown that, in metallocene and postmetallocene catalysts, the same construction principles of immobilization are preserved as in the case of first-generation metal-complex catalysts. The possibility of isolating and studying active intermediates offered by the polymer support and the effect of immobilization on the molecular design of polymer systems are discussed.     

烯烃配位聚合二十年

聚烯烃树脂是消费量最大的合成树脂种类,性能优异,用途广泛。二十多年来,烯烃配位聚合技术取得了突飞猛进的发展,在催化剂、聚合方法、聚合工艺方面都有重大突破。本文综述了二十多年来烯烃配位聚合的研究发展情况,包括Ziegler-Natta催化剂,茂金属催化剂,非茂金属催化剂,配位聚合机理,功能化聚烯烃的制备,原位共聚制备LLDPE,原位聚合制备纳米复合材料,活性配位聚合以及Spherizone工艺等方面的成就。     

Ethylene polymerization and ethylene-1-hexene copolymerization over immobilized metallocene catalysts

Ethylene polymerization and ethylene-1-hexene copolymerization in the presence of metallocene catalysts based on Cp₂ZrCl₂, rac-Et(Ind)₂ZrCl₂, rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂, and rac-Me₂Si(2-Me-4-Ph-Ind)₂HfCl₂ been investigated. The catalysts have been immobilized on montmorillonite (MMT) containing methylaluminoxanes (MMT-H₂O)/AlMe₃ or isobutylaluminoxanes (MMT-H₂O)/ Ali-Bu₃ synthesized directly on the support surface. The immobilized catalysts, with the general formula (MMT-H₂O)/AlR₃/Zr(Hf)-cene, show a high activity comparable with the activity of the respective homogeneous systems, which depends on the nature of the metal and on the metallocene composition and structure. The catalytic properties of the metallocene systems depend strongly on the nature of the activator as a component of the catalytic complex. (MMT-H₂O)/Ali-Bu₃ is a more effective activator of the hafnocene precatalyst in the polymerization processes than oligomeric methylaluminoxane or methylaluminoxane synthesized on the support. The immobilization of the metallocenes on (MMT-H₂O)/AlR₃ leads to an increase in the molar mass of polyethylene and ethylene-1-hexene copolymers relative to the molar mass of the polymers synthesized using the respective homogeneous systems. The immobilized metallocene catalysts display high selectivity toward the insertion of a higher α-olefin (1-hexene) into the polymer chain, retaining this important property of their homogeneous counterparts.     

Unusual ethylene polymerization results with metallocene catalysts supported on silica

With the development of methods to support metallocenes and methylaluminoxane cocatalysts on suitable carriers, it became possible to combine the specific advantages of homogeneous metallocene catalysis with those of heterogeneous Ziegler catalysts in olefin polymerization. By means of ethylene polymerization it could be shown that the method of supporting methylaluminoxane and metallocene on porous silica has a substantial influence on the progress of polymerization. In particular, fragmentation of catalyst particles during polymerization can be circumvented, maintaining the catalyst activity, if active catalyst sites are being generated on the particle surface only. A method of preparation for such newly designed supported metallocene catalysts is presented, where the active catalyst sites are located exclusively on the particle surface. Furthermore, the kinetics of ethylene polymerization and morphology properties prior to and after polymerization are discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 677–682, 1999     

Supported Zr-and Hf-cene Catalysts for Propylene Polymerization

The supported metallocene catalysts were obtained on the layered silicate montmorillonite (MMT), using AlMe₃ and AliBu₃ for synthesis of alkylaluminoxane directly on a support surface, followed by metallocene supporting. It was shown that the MMT-H₂O/AliBu₃ forms with ansa-Zr-cenes of C₁ and C₂-symmetry the significantly more active supported metal-alkyl complexes in propene polymerization, than MMT-H₂O/AlMe₃. The MMT-H₂O/AliBu₃ is the effective activator of the ansa-Hf-cenes, in contrast to MAO and MMT-H₂O/AlMe₃, giving the high active supported catalysts for synthesis of isotactic and elastic polypropene. The character of influence of metallocene fixation on support on the isotactic pentad [mmmm] content in polymer, compared to homogeneous analogues, depends on the metallocene nature. The introduction of borate Ph₃CB(C₆F₅)₄ in the case of both Zr-cene and Hf-cene catalysts increases significantly the activity at the reduced ratio of Al/Zr, Hf (100–500 instead of 2000–3000) and stabilizes the catalytic complexes.     

Polymerization mechanism for in situ supported metallocene catalysts

The polymerization of ethylene was carried out with a novel in situ supported metallocene catalyst that eliminated the need for a supporting step before polymerization. In the absence of trimethyl aluminum (TMA), in situ supported Et[Ind]₂ZrCl₂ was not active, but the addition of TMA during polymerization activated the catalyst. Et[Ind]₂Zr(CH₃)₂ was active even in the absence of TMA, whereas the addition of TMA during polymerization enhanced the catalytic activity. The polymerization‐rate profiles of the in situ supported metallocene catalysts did not show rate decay as a function of time. A polymerization mechanism for the in situ supported metallocene catalysts is proposed for this behavior. During polymerization, the in situ supported metallocene catalysts may deactivate, but homogeneous metallocene species present in the reactor may form new active sites and compensate for deactivated sites. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 462–468, 2000     

Morphology Evolution in the Early Stages of Olefin Polymerization

The olefin polymerizations were carried out by using silica supported metallocene/MAO catalysts and MgCl₂ supported Ziegler-Natta catalysts under mild reaction conditions and stopped at very low yield. The surface and cross sectional morphology of the polymer particles were characterized by using scanning electron microscopy (SEM). A homogeneous distribution of (co)catalyst on the support material is a prerequisite condition to get a homogeneous fragmentation and uniform polymer particle morphology. In the present work the catalysts show two different fragmentation behaviors. They can gradually fragment from the outer to the inner surface of the catalyst particle, or instantaneously break up into a large amount of small sub-particles at the beginning of the polymerization. The incorporation of comonomer does not change the general catalyst fragmentation scheme but delays the catalysts break-up progress.     

Ethylene polymerization and copolymerization with hexene-1 on supported metallocene catalysts based on (C<Subscript>5</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>Zr and methylaluminoxane

New supported metallocene catalysts based on tetrakis(cyclopentadienyl)zirconium + methylaluminoxane (MAO) were prepared and tested for ethylene polymerization and copolymerization with hexene-1. It was shown that silica gel of the Davison 952 brand is the best support for such catalysts. The maximum catalyst activity was achieved on the support impregnated with the (C₅H₅)₄Zr-MAO complex. The addition of hexene-1 into the liquid phase resulted in acceleration of polymerization and an increase in the product yield. The morphological, rheological, and other properties of polymers and copolymers were studied. The test catalytic system can be used for manufacture of low-, medium-, and high-density polyethylenes with various stress-strain characteristics.     

Hydrogen transfer reactions of supported metallocene catalysts

The evolution of methane from methylaluminoxane (MAO) solutions is enhanced in the presence of homogeneous metallocenes. This reaction serves as a model for the deactivation of metallocene catalysts. By supporting different metallocenes on a silica/MAO carrier the deactivation reaction by alpha-hydrogen transfer among metallocene active sites and aluminum alkyls can be suppressed. The suppression of alpha-hydrogen transfer is proven for different Al/Zr ratios and by near independence of the polymerization activity on the catalyst aging time, after reaching maximum activity. Aluminum alkyls and MAO leach Cp₂ZrCl₂ from the carrier, the leached metallocene is only active in polymerization if MAO is present.     

Heterogenized methylaluminoxane and isobutylaluminoxane as activators for metallocene catalysts

Heterogenized alkylaluminoxanes prepared in situ on the montmorillonite (MMT) surface by the partial hydrolysis of AIR₃ with water of the support are effective activators for metallocenes. The thermal destruction of isobutylaluminoxane molecules in the MMT-H₂O/Al(i-Bu)₃ system has been studied by the temperature-programmed desorption method coupled with mass spectrometry (TPD-MS). The process begins at a lower temperature and is more complicated than the destruction of methylaluminoxane (MAO) in MMT-H₂O/AlMe₃. Isobutyl-substituted aluminoxane and the ansa-metallocene Me₂Si(Ind)₂ZrCl₂ form metal-alkyl complexes that are more active in propylene polymerization than methyl-substituted aluminoxane. The TPD-MS study of the initial stages of gas-phase ethylene and propylene polymerization shows that the nature of the metallocene in the heterogenized metallocene catalysts is an essential factor in the distribution of active sites by the activation energy of the thermal destruction of active Zr-C bonds.     

Polymacromonomers with polyolefin branches synthesized by free-radical homopolymerization of polyolefin macromonomer with a methacryloyl end group

Polymacromonomers with polyolefin branches were successfully synthesized by free-radical homopolymerization of polyolefin macromonomer with a methacryloyl end group. Propylene-ethylene random copolymer (PER) with a vinylidene end group was prepared by polymerization using a metallocene catalyst. Then, the unsaturated end group was converted to a hydroxy end group via hydroalumination and oxidation. The PER with the hydroxy end group was easily reacted with methacryloyl chloride to produce methacryloyl-terminated PER (PER macromonomer; PERM). The free-radical polymerization of thus-obtained PERM was done using 2,2′-azobis(isobutyronitorile) (AIBN) as a free-radical initiator. From NMR analyses, the obtained polymers were identified as poly(PERM). Based on gel permeation chromatography (GPC), the estimated degree of polymerization (D_p) of these polymers were about 30. Thus, new class of polymacromonomers with polyolefin branches was synthesized.     

Binary metallocene supported catalyst for propylene polymerization

The binary silica supported catalyst system comprising the Cp₂ZrCl₂ and SiMe₂(Ind)₂ZrCl₂ metallocene compounds was prepared with different immobilization methods and evaluated at different propylene polymerization conditions. The performance results of the homogeneous isolated catalysts and also the homogeneous catalyst mixture were also included for comparison. High activities were obtained with the supported systems and the molecular weight of the produced polypropylene was invariably higher than that obtained using the homogeneous precursor.     

Recent progress on olefin polymerization catalysts

Recent progress on metallocene catalysts is reviewed. This consists for the main part of research activities in metallocene catalysts and their polymerization performances (ethylene polymerization, propylene polymerization, styrene polymerization). In addi-tion, the computational design of metallocene catalysts and the commercial status of metallocene technologies in Japan are described.     

New materials from new catalysts

The polyolefins, especially polypropylene and polyethylene, industry of today is very different from that of 10 years ago. The development of highly active and stereospecific catalysts, represented by Ti/Mg supported catalysts, have made the gas-phase polymerization process practical. The trend in catalyst development is shifting from an emphasis on improving the stereospecificity and activity toward improving the polymer physical properties, processability and morphology. Many hybrid thermoplastic olefins, such as high-impact copolymers, propylene–ethylene–butene terpolymers, and very low density polyethylene, have already been developed by utilizing the features of the gas-phase polymerization process. These hybrid thermoplastic olefins cover a very broad range of products. They cannot be clearly identified as polyethylenes, polypropylenes or elastomers. Incidentally, metallocene catalysts for polyolefins have been under development for the past 15 years, and are now in the early stage of commercialization. These catalysts differ significantly from the conventional heterogeneous catalysts. They can polymerize not only ethylene, propylene and other linear α-olefins, but also styrene, cycloolefins and functional monomers In addition, they can control the microstructure of polymer molecules by varying the transition metals and the cyclopentadienyl ligands. Because of these features, we have to be confident that the development of metallocene catalysts, or more widely homogeneous catalysts, may be a dominant force throughout the 1990s in the polyolefin industries.