Current studies on novel, metallocenebased catalysts for the polymerization of α-olefins have far-reaching implications for the development of new materials as well as for the understanding of basic reaction mechanisms responsible for the growth of a polymer chain at a catalyst center and the control of its stereoregularity. In contrast to heterogeneous Ziegler–Natta catalysts, polymerization by a homogeneous, metallocene-based catalyst occurs principally at a single type of metal center with a defined coordination environment. This makes it possible to correlate metallocene structures with polymer properties such as molecular weight, stereochemical microstructure, crystallization behavior, and mechanical properties. Homogeneous catalyst systems now afford efficient control of regio- and stereoregularities, molecular weights and molecular weight distributions, and comonomer incorporation. By providing a means for the homo- and copolymerization of cyclic olefins, the cyclopolymerization of dienes, and access even to functionalized polyolefins, these catalysts greatly expand the range and versatility of technically feasible types of polyolefin materials. For corrigendum see DOI: 10.1002/anie.199513681 相似文献
The previously developed kinetic scheme for olefin polymerization reactions with heterogeneous Ziegler–Natta catalysts states that the catalysts have several types of active centers which have different activities, different stabilities, produce different types of polymer materials, and respond differently to reaction conditions. In the case of ethylene polymerization reactions, each type of center exhibits an unusual chemical feature: a growing polymer chain containing one ethylene unit, Ti—C2H5, is unusually stable and can decompose with the formation of the Ti—H bond. This paper examines quantitative kinetic ramifications of this chemical mechanism. Modeling of the complex kinetics scheme described in the Scheme demonstrates that it correctly and quantitatively predicts three most significant peculiarities of ethylene polymerization reactions, the high reaction order with respect to the ethylene concentration, reversible poisoning with hydrogen, and activation in the presence of α‐olefins. 相似文献
The following criteria are proposed to judge whether a coordination polymerization may be diffusion controlled or not: (1) If the number-average molecular weight and polydispersity of the polymer calculated from kinetic rate constants as a function of time agree with the experimental values, the polymerization is not diffusion controlled. (2) The polymerization may be diffusion controlled if the Thiele modulus, the ratio of the characteristic diffusion time to the characteristic reaction time, is much greater than unity; if it is much smaller than unity, the polymerization is reaction controlled. (3) If an initial linear dependence of rate of polymerization on catalyst concentration changes over to a square-root dependence, the polymerization may be diffusion limited. (4) The polymerization is likely to be diffusion limited if the instantaneous rate of polymerization is proportional to the rate of particle growth when the proportionality coefficient is the surface area of the particle. Criterion (1) is a necessary and sufficient condition as stated, as its converse is not true. All the other criteria are merely necessary but not sufficient conditions. The established Ziegler–Natta catalysts have activities too low to cause diffusion limitation; the Phillips catalyst system is likely to be diffusion limited. The polydispersity of polyolefins produced with Ziegler–Natta catalysts are not the consequence of diffusion control but are the characteristics of the catalysts in their kinetics of initiation, propagation, chain transfer, and termination. 相似文献
Russian Journal of Applied Chemistry - The suspension polymerization in octafluorobutane, initiated by Ziegler–Natta catalyst system, has been used to synthesize ultra-high molecular weight... 相似文献
This article proposes a method to quantify the polymerization kinetics of ethylene and α‐olefins with commercial TiCl4/MgCl2 Ziegler–Natta catalysts. The method determines the leading apparent polymerization kinetic constants for each active site in a Ziegler–Natta catalyst by simultaneously fitting the instantaneous polymerization rate, cumulative polymer yield, and polymer molecular weight distribution measured at different times during a series of semi‐batch polymerization experiments. This approach quantifies the behavior of olefin polymerization with multisite catalysts using the least number of adjustable parameters needed to consistently model polymerization kinetics and polymer microstructural data.
The study of new catalytic systems is critical in order to develop improved and cost effective polymerization processes. One of the methods to evaluate the performance of a catalytic system is by means of bench scale reactors. Despite its difference in size with large scale industrial plants, bench scale reactors have proved to be a valuable tool to understand the behavior of the catalytic system during the polymerization. In this work, a method to estimate the kinetic parameters of propylene polymerization over a conventional Ziegler Natta catalyst is evaluated. Thus, it was possible to set up a semi-empirical model to correlate the reaction yield with the polymerization time, the hydrogen content in the reactor and the reaction temperature. This model proves to be useful to evaluate the performance of a catalytic system within the range of normal operating conditions. A brief study on the particle size distribution of the products is also carried out. 相似文献
In the previous paper we calculated the most stable structure of the catalyst and cocatalyst of metallocene catalyst systems using molecular dynamics and molecular mechanics. In this paper we postulate the active site of the heterogeneous Ziegler–Natta catalyst, and analyze it by the same methods to clarify the main factors that control the activity and molecular weight distribution of the heterogeneous catalyst systems. The roles of the external donor were also considered, and we found that the interaction energy between an external donor and the active site of the catalyst, as well as the structural factors of the external donor itself, are strongly related to both activity and molecular weight distribution. These results reveal that molecular dynamics and molecular mechanics calculations are also effective methods to screen the heterogeneous catalyst systems. 相似文献
The chain transfer reaction by hydrogen in the initial stage of propene polymerization with MgCl2-supported Ziegler catalyst was studied by means of the stopped-flow polymerization. The yield and molecular weight of polypropene produced in the initial stage were not affected by hydrogen. Thus, the method was successfully applied to find the region in which hydrogen does not act as a chain transfer reagent. On the other hand, a chain transfer reaction proceeded in the initial stage of polymerization by using Zn(C2H5)2. Furthermore, when the catalyst was treated with Al(C2H5)3 before polymerization, the molecular weight of the produced polymer was decreased by using hydrogen, indicating that it acted as a chain transfer agent for the catalyst modified by pre-treatment. 相似文献
There has been continuing interest in the possible role of insoluble polymer products forming a barrier reducing rate of diffusion of monomer to the active site to cause decrease in rate of polymerization and broadening of molecular weight distribution. This possibility is more acute the higher the catalytic activity. We have now shown that diffusion limitation is unimportant for the MgCl2 support high activity Ziegler–Natta catalyst by comparing its polymerization of propylene to isotactic insoluble polypropylene and of decene-1 to isotactic soluble polydecene. The rate constant of propagation is about eight times greater for propylene while the rate constants of termination, i.e, decay of Rp, are comparable for the two monomers. 相似文献
This study focuses on gas-phase polymerization of ethylene using the titanium-based Ziegler–Natta catalysts prepared from different magnesium sources including MgCl2 (Cat A), magnesium powder (Cat B), and Mg(OEt)2 (Cat C). During polymerization, different cocatalysts were also used. It was found that Cat C with triethylaluminum as a cocatalyst exhibited the highest activity. This was likely attributed to optimal distribution of active sites on the catalyst surface. It can be observed by increased temperature in the reactor due to highly exothermic reaction during polymerization. By the way, the morphologies of the polymer obtained from this catalyst were spherical, which is more preferable. Besides the catalytic activity, crystallinity and morphology were also affected by the different magnesium sources used to prepare the catalysts. 相似文献