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Chain Transfer Mechanisms

Initiation and termination mechanisms in palladium catalyzed copolermizations

  • Chapter
Catalytic Synthesis of Alkene-Carbon Monoxide Copolymers and Cooligomers

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 27))

Abstract

Chain initiation and termination immediately came into focus when the first well-defined and relatively fast palladium catalysts for copolymerization, containing as a characteristic weakly coordinating anions, were introduced in 1982 [1]. The palladium chloride based catalysts studied in the sixties and seventies required high temperatures and usually led to palladium metal formation, in spite of the high carbon monoxide pressures used [2]. As we will see, initiation plays a key role and addition of an initiator, an alkylating agent for instance, would have turned these catalyst systems into highly active ones. The initiation process took place by chance due to the presence of water [1] or the use of methanol as the solvent in search of a methoxycarbonylation catalyst for ethene based on palladium complexes of diphosphines [3]. Taking initiation and alternating propagation for granted the first concern was how to control the molecular weight, or in other words how does chain termination take place and how can it be controlled. Ideally, after chain termination the palladium metal center starts a new cycle, as it is important in polymer catalysis to make more than one chain per metal center. This is called chain transfer. In alkene polymerization two important mechanisms occur for chain transfer, the first being β-hydride elimination, after which the metal hydride formed can start a new polymer chain, and the second being hydrogenolysis of the metal-alkyl chain using dihydrogen, after which also the metal hydride can act as initiator of the next chain. The second mechanism is more useful, as a saturated, less reactive end-group is formed; the rate of termination (= chain transfer), and thus the molecular weight, can be controlled by the concentration of the chain transfer agent, H2

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  1. Institute of Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, the Netherlands

    Piet W. N. M. van Leeuwen

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  1. Department of Chemistry, The Pennsylvania State University, USA

    Ayusman Sen

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van Leeuwen, P.W.N.M. (2003). Chain Transfer Mechanisms. In: Sen, A. (eds) Catalytic Synthesis of Alkene-Carbon Monoxide Copolymers and Cooligomers. Catalysis by Metal Complexes, vol 27. Springer, Boston, MA. https://doi.org/10.1007/978-1-4419-9266-6_5

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