Macromolecular Complexes as Chemical Reaction Catalysts

The wide potential applications of catalysis by macromolecular compounds have aroused universal interest in this relatively new branch of chemical science: the number of publications devoted to this problem has been growing continuously since the 1950's. Thus, many papers have dealt with the use of sulphonic acid resins as catalysts for hydrolysis and esterification, hydration and dehydration, alkylation, and also various condensations (see review by Polyanskii, recent Japanese work , etc.). A substantial fund of knowledge has accumulated also on the use of macromolecular catalysts and initiators in polymerisation reactions. For example, the above sulphonic acid resins have been used as polymerisation catalysts for isopentene, butene, dienes and vinyl alkyl esters. Macromolecular radicals obtained by chain transfer reactions, illumination, mechanical methods, or by chemical changes of reactive groups are already used extensively in the synthesis of graft or block copolymers. These and other polymer systems can be synthesised also on macromolecular anions obtained as macromolecular Ziegler–Natta catalysts, macromolecular anion-radicals, or dianions, on macromolecular organometallic compounds of the polylithiumpolystyrene or polylithiumpolyethylene type, etc.
Papers on the catalysis of reactions by macromolecular complexes relate to the same field of research. The present review, without attempting to be fully comprehensive, deals with the most important papers (published up to 1968) on the catalysis of organic and of inorganic reactions by macromolecular complexes. For comparison, low-molecular-weight complexes are considered in a number of instances. 84 references.