Abstract
This paper is concerned with (a) the thermodynamic and kinetic binding sites for Cr(0) in polyimides, and (b) the application of the binding of metals to specific sites on the polyimide backbone to the synthesis of polymer trapped chromium and iron oxide nanoclusters (size < 1.5 nm). In the first part, the organometallic products obtained by the reaction of Cr(CO)3(MeCN)3 or Cr(CO)6 with a number of compounds that mimic the polyimide backbone were identified. A π-arene complex was formed in each case indicating that Cr(0) prefers to form π-arene complexes (even with electron deficient arene rings) rather than react with the oxygen functionalities present. Furthermore, the tendency to form a π-arene complex increases with increasing electron density on the ring. The first part also describes the synthesis and x-ray crystal structure of a charge-transfer complex of Cr(CO)6 with pyromellitic dianhydride — one of the building blocks of polyimides. The second part outlines the synthesis of polyimide-trapped metal oxide nanoclusters. Cr(C6H6)2 or Fe3(CO)12 was added to polyamic acid solutions. Following thermal curing, polyimide films containing a homogeneous dispersion of nanoclusters (size < 1.5 nm) of Cr2O3 or α-Fe(O)(OH) were obtained. Both SEM and SIMS depth profile indicated that the usually observed migration of the dopant to the polymer surface had not occurred.
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Sen, A., Nandi, M., Conklin, J.A. (1991). Molecular Level Metal and Ceramic/Polymer Composites: Synthesis of Metal and Metal Oxide Containing Polyimides and its Relevance to Polymer Metallization. In: Mittal, K.L. (eds) Metallized Plastics 2. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-0735-6_3
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