Ethylene olefin insertion, polymerization reaction

By performing excellent model reactions [144], Grubbs and his co-workers demonstrated direct olefin insertion into an M-C bond. Thus, complex 115 was treated with AlEtCl2 to give complex 116, whose decomposition afforded methylcyclopentane. Under the same conditions, the polymerization of ethylene took place. In this way, the insertion of a-olefins into a Ti-C single bond in a model Ziegler-Natta catalyst system was directly observed (Eq. 9). 

The kinetics of olefin polymerization are the subject of several studles>104,153-156,162,182,221,226,240,241,246,252,255,266,28 12 and of an excellent book by Keii.17 The most relevant studies will be discussed below. However, we first note that the precise description of the kinetics of catalytic olefin polymerization under industrially relevant polymerization conditions has proved to be very difficult. For a given catalytic system, one has to identify all possible insertion, chain-release, and chain-isomerization reactions, and their dependence on the polymerization parameters (most importantly, temperature and monomer concentration). Once the kinetic laws for each elementary step have been determined, they have to be combined in one model in order to be able to predict the catalyst performance. This has been attempted for both ethylene and propylene polymerizations. The case of propylene polymerization with a chiral, isospecific zirconocene is shown in Figure 14.162... 

Described in this paper is a model system - one in which well-characterized lanthanide complexes exhibit high catalyst activities for ethylene polymerization but where the corresponding oligomerization of propene is sufficiently slowed so that stepwise insertion of the olefin can be studied quantitatively and all important intermediates observed or isolated. Emphasized in this paper is the effect of added Lewis acids and bases on the rate of olefin insertions, and comparison between ethylene and propene reactions. The catalysts, of general structure M(ri -Cp )2CH3 L (M = Yb, Lu ... 

The /3-elimination, a side reaction leading to the chain transfer, as shown in Fig. 17, has a quite high endothermicity of about 52.8 (Ti), 45.6 (Zr), and 48.5 (Hf) kcal/mol and is an unfavorable path. The reverse reaction of olefin insertion into an M-H bond has a very low barrier. Based on the above-mentioned results, YKM [52] have concluded that ethylene polymerization with these cationic calalysts can occur rapidly, resulting in high-molecular-weight polymer, most favorably in the reaction with Hf. 

Most reaction models which describe the mechanism of diene polymerization by Nd catalysts have been adopted from models developed for the polymerization of ethylene and propylene by the use of Ti- and Ni-based catalysts systems. A monometallic insertion mechanism which accounts for many features of the polymerization of a-olefins has been put forward by Cossee and Arlman in 1964 [624-626]. Respective bimetallic mechanisms date back to Patat, Sinn, Natta and Mazzanti [627,628]. The most important and generally accepted mechanisms for the polymerization of dienes by Nd-based catalysts are discussed in the following. 

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