Synthesis metal containing monomers

Other important methods of synthesis of coordination compounds are discussed in detail [1,3,10,11,53,201,202,206,207,316,318,322,690]. In this respect, we emphasize the synthesis of metal-polymers [690,691] and preparation of complexes in the solid phase (mechano- or tribosynthesis) [10,201,202,206]. Additionally to the above-described techniques, the general methods and principles of synthesis of coordination compounds are used to obtain metal-polymers (immediate interaction of polymer ligands and metal salts, template electrosynthesis, polymer-analogous transformations). The last method consists of the polymerization of metal-monomers (metal-containing monomers) and fixation of metal complexes on the polymer... 

A.D. Pomogailo, VS. Savost yanov, Synthesis and Polymerization of Metal Containing Monomers, CRC Press, Boca Raton, 1994. 

While the types of MCMs described earlier have already received comparatively wide popularity in polymerization practice, polymers based on metal-containing monomers of the chelate type have only been prepared more recently. The methods of assembly of such MCMs, i.e. the simultaneous formation of the ligand and the corresponding complex, have been substantially developed. The synthesis of MCMs from /7-aminostyrene, 2-formylpyrrole and Cu(II) or Co(III) salts is an example of such a method. The last approach is especially characteristic of the preparation of MCMs with macrocyclic chelate nodes, in particular, from porphyrins, phthalocyanines and other macrocycles with exocyclic multiple bonds. It is worth noting that traditional methods of chelation are used for preparing MCMs when scientists want to ensure strong multicenter fixation of metals into monomer molecules, and, thus, into (co)polymers. 

Thus, the synthesis of metal-containing monomers is a well-developed field of the science which has appeared as a branch of inorganic, coordination and organometallic chemistry. The chemist can practically obtain all types of MCM. Characteristic representatives are given in Fig. 4-5. 

At present, several thousand metallopolymers have been described, although the part of those obtained by polymerization and l lopolymerisation of metal-containing monomers is not great. Nevertheless, the procedures of synthesis of over 200 metallomonomers are given in the monograph [124]. In this book we restrict ourselves to preparative methods of synthesis only of some main representatives of metal-containing monomers and their polymers. 

A rare case is copolymerization of several different MCMs. Ihe resulting polymers can contain mixed units of various types. This is particularly true for the development of high-temperature superconducting (HTSC) ceramics that are based on synthesized prepolymers. One of the methods that is used is the copolymerization of MCM acrylates (and perhaps maleinates) or acrylamide complexes ofY, Ba, or Cu and the synthesis of superconducting bismufli cuprates (e.g., Bi2Sr2Ca -i Cu 02n+4-5 where n = l-3) by copolymerization of the corresponding metal-containing monomers. Thermolysis of these polymeric precursors affords a finely... 

This chapter describes the synthesis and properties of a number of classes of polymers containing metal coordination complexes in their structures. These polymers are prepared by polymerization reactions of metal-containing monomers and through metal coordination reactions. Schiff base-containing polymers (5) were one of the earUest classes of coordination polymers examined. Polymers incorporating macro-cycUc porphyrins and phthalocyanines (7) in their backbones and sidechains are known to exhibit interesting optical and electrical properties. The best-studied classes of metal-containing polymers contain bipyridyl and other related units coordinated to metal ions (8). 

Andrianov and Zhdanov have developed a method for the synthesis of polymers containing heterochain and carbon-chain units by free-radical copolymerization of metal-containing polyorganosiloxanes bearing a pendant vinyl group with vinyl monomers. The copolymers thus obtained display increased thermal stability and can be used for the production of laminated plastics, adhesives and other valuable materials 53),... 

The majority of inorganic reactions can be placed into one of two broad classes (1) oxidation-reduction (redox) reactions including atom and electron transfer reactions and (2) substitution reactions. Terms such as inner sphere, outer sphere, and photo-related reactions are employed to describe redox reactions. Such reactions are important in the synthesis of polymers and monomers and in the use of metal-containing polymers as catalysts and in applications involving transfer of heat, electricity, and light. They will not be dealt with to any appreciable extent in this chapter. 

Although most metal-containing polythiophenes have been synthesized by electropolymerization on an electrode surface, there are many reasons to chemically synthesize these polymers. Chemical synthesis may allow isolation of soluble polymers, enabling complete solution characterization (GPC, light scattering, NMR, etc.) and facilitating conductivity studies. Moreover, it can enable improved thin-film preparation and film deposition onto nonconducting substrates. Finally, monomers that are unsuitable for electropolymerization may be polymerized by chemical methods. 

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