Polymerization of Cycloalkanes

An attempt will be made in this chapter to review those structural parameters that play a critical role in the ROP of cycloalkanes. First, the thermodynamic parameters that govern the polymerizability of these monomers as a class will be briefly analyzed after which details of the various cycloalkyl monomers whose polymerizations have been described in the literature will be provided. For this, we will use mostly tabulated data. 

Handbook of Ring-Opening Polymerization. Edited by P. Dubois, 0. Coulembier, and J.-M. Raquez Copyright 2009 WILEY-VCH Veriag GmbH Co. KGaA, Weinheim iSBN 978-3-527-31953-4 

It should be noted that reviews covering specific areas of this chapter have appeared periodically [5, 6], dealing mostly with their authors findings on the polymerization of bicyclobutanes [7-9], cyclopropanes [1,3,10-12] and propellanes [13-16]. These reviews are highly recommended as a further source of information, not only for the polymerization of monomers but also for the properties of the polymers thus obtained. 

Nonetheless, and in sharp contrast to the polymerization of heterocycles, such achievements-as measured by the number of new stractures added to the pool of available monomers-have been somewhat hmited. This success rate is not surprising in itself if one considers the difficulty of the reaction involved, namely a C—C bond cleavage. Carbon—carbon single bonds are notoriously difficult to break as a rule, they do not react with free-radicals and rarely participate in reactions with electrophiles and nucleophiles [20]. In addition, as the two atoms making the bond are identical, no polarization is introduced into the system. 

Structure-Reactivity Reiationships Based on a Comprehensive Survey of the Current Literature 

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It is now well established that ring-opening polymerization of cycloalkanes and bicycloalkenes, initiated with olefin metathesis catalysts, is propagated by metal carbene complexes (1). 

Penelle J. Polymerization of cycloalkanes. In Dubois P, Coulembier O, Raquez J-M, editors. Handbook of Ring-Opening Polymerization. Weinheim, Germany Wiley-VCH 2009. p 329. 

Part 2 includes chapters on specific classes of cyclic monomers and their polymerization mechanisms and kinetics, their main (co)polymer architectures and related products, as well as current and future applications. Hence, siloxane-con-taining and sulfur-nitrogen-phosphorus-containing polymers are described in Chapters 3 and 4, respectively, while the polymerization of cyclic depsipeptides, ureas and urethanes, of polyethers and polyoxazolines, and of polyamides are detailed in Chapters 5, 6 and 7, respectively. Chapters 9, 10, 11 and 12 include details of polyesters prepared from either P-lactones, from dilactones, from larger lactones and from polycarbonates, while the polymerization of cycloalkanes is described in Chapter 13. It should be noted that, slightly out of place . Chapter 8 covers the subject of ring-opening metathesis polymerizahon. 

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