Alternating copolymerization of alkenes and carbon monoxide

Reppe and Magin disclosed in 1951 that an olefinic compound, typically ethene reacted with carbon monoxide at 190 bar (C2H4 CO = 1 1) in the 

Tokitoh, N. Yoshimura, M. Tamura, Proc. SHHC-7, Tokyo, 1992, P90 

Yoshimura, Y. Tokitoh, M. Matsumoto, M. Tamura, Nippon Kagaku Kaishi 1993, 

Yoshimura, in Aqueous-Phase Organometallic Catalysis (B. Cornils, W. A. Herrmann, eds.), Wiley-VCH, Weinheim, 1998, p. 408 

Cermdk.M. KviCalovd,V. Blechta, Collect. Czech. Chem. Commun. 1997,62,355 

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PALLADIUM-CATALYZED ALTERNATING COPOLYMERIZATION OF ALKENES AND CARBON MONOXIDE... 

Drent, E. Budzelaar, P. H. M. PaUadium-catalyzed alternating copolymerization of alkenes and carbon monoxide. Chem. Rev. 1996, 96, 663-682. 

In a patent filed as early as 1948, Reppe and Magin described the reaction of ethylene with carbon monoxide in the presence of an aqueous solution of potassium nickel(II) cyanide at 150°C and 150 bar [4], Along with propionic acid and diethyl ketone, higher molecular weight solid polyketones were obtained. The alternating copolymerization of alkenes with carbon monoxide has received continued industrial and academic interest, one reason being the low cost of carbon monoxide as a monomer [5],... 

Kamer, P.C.J., Goubitz, K., Fraanje, J., Lutz, M. and Spek, A.L. (2003) Alcoholysis of acylpalladium(II) complexes relevant to the alternating copolymerization of ethene and carbon monoxide and the alkoxycarbonylation of alkenes the importance of cis-coordinating diphosphines. Journal of the American Chemical Society, 125, 5523. 

The copolymerization of alkenes with carbon monoxide has attracted the attention of chemists for many years [1]. Following the commerciahzation of Carilon, an alternating olefin carbon monoxide terpolymer based on ethene and small amounts (5-10%) of propene (Scheme 8.1, 1), by Shell [2, 3] in the 1990s interest in the identification of new and more active catalysts and of the stereochemical characteristics of the reaction has grown. 

There is a tendency toward alternation in the copolymerization of ethylene with carbon monoxide. Copolymerizations of carbon monoxide with tetrafluoroethylene, vinyl acetate, vinyl chloride, and acrylonitrile have been reported but with few details [Starkweather, 1987]. The reactions of alkenes with oxygen and quinones are not well defined in terms of the stoichiometry of the products. These reactions are better classified as retardation or inhibition reactions because of the very slow copolymerization rates (Sec. 3-7a). Other copolymerizations include the reaction of alkene monomers with sulfur and nitroso compounds [Green et al., 1967 Miyata and Sawada, 1988]. 

Nozaki, K. Shibahara, R Elzner, S. Hiyama, T. Alternating copolymerization of w-perfluoroalkyl-1-alkenes with carbon monoxide catalyzed by homogeneous and polymer-supported Pd-complexes. Can. J. Chem. 2001, 79, 593-597. 

Drent, E. van Broekhoven, J. A. M. Doyle, M. J. Wong, P. K. Palladium Catalyzed Copolymerization of Carbon Monoxide with Alkenes to Alternating Polyketones and Polyspiroketals. Fink, G. Muelhaupt, R. Brintzinger, H. H. Eds. Ziegler Catal. Springer, Berlin, 1995, pp 481 496. 

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