Polymerization metal-containing monomers

Well-defined nanoclusters (w 10-100 A diameter) of several metals have been prepared via the polymerization of metal-containing monomers. The synthetic approach involves the block copolymerization of a metallated norbornene with a hydrocarbon co-monomer which is used to form an inert matrix. Subsequent decomposition of the confined metal complex affords small clusters of metal atoms. For example, palladium and platinum nanoclusters may be generated from the block copolymerization of methyl tetracyclododecane (223) with monomers (224) and (225) respectively. 10,611 Clusters of PbS have also been prepared by treating the block copolymer of (223) and (226) with H2S.612 A similar approach was adopted to synthesize embedded clusters of Zn and ZnS 613,614... 

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... 

I, vinylruthenocene, 66, vinylosmocene, and the T)5-(vinylcyclopentadienyl)metal carbonyl monomers in radical-initiated polymerizations summarized in Scheme 1.1 no longer exists for anionically initiated addition polymerizations. Styrene is readily initiated by such anionic species as BuLi and Na1 Naphth. Living anionic styrene homopolymerizations and block copolymerizations have been extensively commercialized for many years (e.g., Kraton thermoplastic elastomers). However, the exceptionally electron-rich vinyl metal-containing monomers 1, 8-18, 24-30, and 66 were never successfully initiated by anionic systems in our laboratory despite many attempts. In these systems, the a-carbocations are very stable, but the a-carbanions are quite unstable. Thus, the addition of an anion to tbe vinyl function of these monomers is unfavorable. 

Polymerization of metal-containing monomers is often more complicated, but generally gives purer polymer than postpolymerization metalation. The former method allows 100% metalation of coordination sites in the polymer, whereas the latter method usually results in only partial... 

Some other works that we would like to mention studied the kinetics effects in FP [85], the influence of the gel effect on the propagation of thermal frontal polymerization waves [28], the use of complex initiators as a means to increase the degree of conversion of the monomer [30], and FP of metal-containing monomers [3]. 

V. Barelko, a. Pomogailo, G. Dzhardimalieva, S. Evstratova, A. Rozenberg, and I. XlFIzyKtyP), The autowave modes of solid phase polymerization of metal-containing monomers in two- and three-dimensional fiberglass-filled matrices, Chaos, 9 (1999), pp. 342-347. 

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

Chapter 3 concentrates on different aspects of the formation of macromolecular metal complexes (MMCs) by interaction of a macromolecular ligand with a metal compound MX . Such metal-containing macromolecules are classified in Section 1.2.1 as type I. Chapter 4 concentrates on polymerizations of metal-containing monomers. Examples of the binding of MX at macromolecular ligands are given in more detail in Chapter 5. The kinetics and thermodynamics of formation of macromolecular metal complexes of type II, type III and type rv are not known in detail. A few aspects are included in Chapters 6, 7 and 8. 

Polymerization of Metal-Containing Monomers (MCMs) as a Method for Incorporating Metals in Macromolecules... 

Thus, polymerization conversions of metal-containing monomers is a direct method for the s5mthesis of metallopoljaners. Some aspects of the topics we cover are analyzed in the first monographs [1 ] and reviews [5-7]. 

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. 

There are several modes for the frontal polymerization of metal-containing monomers. One such mode is polymerization in a high-temperature burning regime. This method is followed by thermolysis of the products to obtain metal-containing composites that include nano-sized materials. The kinetic peculiarities of high-temperature pyrolysis of the Co(II) acrylamide complex have been studied [84], The rate of the process is approximately satisfied by a first-order equation of autocatalysis (Eq. 4-26), where k = 4.2-10 exp[-24,000/(7 )] (s ), 0 l.910 ... 

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