Macromolecule-metal complex interactions as precursors for the catalytic chemical modification of polymers

Chemical modification of polymers via catalysis has recently emerged as an area of increasing importance in macromolecular chemistry. It provides an efficient synthetic route for the production of novel polymers with desirable physical properties and functional groups which are often inaccessible by conventional polymerization techniques. Diene-based polymers and copolymers are ideal for chemical modification because of the technological importance associated with the parent materials and the reactivities of the double bonds in the polymer chain. In employing organometallic catalysts for such modifications, it has been found that the ligand environment of the catalyst as well as the functionality of the polymer has a profound effect on the nature of the macromolecule-metal complex interaction and the resulting polymer modification. The importance of the macromolecule metal complex interactions and the design of appropriate catalyst systems is illustrated for the hydrogenation, hydroformylation/hydroxymethylation and hydrosilylation of a number of polymers.