Coordination polymer impregnation with

The examples presented in this chapter concern oxides impregnated with aqueous solutions but the field of nonaqueous solvents, which exhibit different coordinative properties, dielectric constant, viscosity, and boiling temperature, and in which precursors like carboxylates and acetylacetonates can be dissolved, should probably be explored more thoroughly. The use of supercritical fluids can also be considered. The fact that more catalysts are being prepared on supports such as carbon fibers or polymers, whose interfacial chemistry is less known than that of oxides, adds interest to these directions of research. 

Another example of promotion by an added metal oxide is Cr/silica incorporating Sn(IV) ions [548,594], Like TiC>2, SnC>2 contains a tetravalent metal ion that can exist in tetrahedral coordination, and has a similar ionic radius. Indeed, SnC>2 and T1O2 are isomorphous. Mixed oxides of SnC>2 and SiC>2 are known to exhibit acidity [595-597], Figure 131 shows the result of adding SnC>2 to the Phillips catalyst. Silica was dried at 200 °C and then treated with an excess of SnCLi vapor. The support was then calcined at 500 °C to remove chloride. It was impregnated anhydrously with chromium and then activated at 500 °C in air. It was quite active in polymerization tests at 105 °C, and the MW distribution of tire polymer is shown in Figure 131. 

Hydrogenation is the most well studied area among immobilized palladium catalysis. While a great majority of the applications focused on the use of support such as alumina and activated carbon, a great diversity of novel support systems have been reported in recent years, aimed at finding a catalyst with a well-characterized coordination sphere and tailor-made activity. Pd(0) catalysts dispersed on crosslinked styrene-divinylbenzene copolymers have been prepared by impregnation of lipophilic complexes followed by reduction with hydrazine. It was found that the functional groups in the polymer as well as polymer particle sizes had a major effect on catalyst activity.t [i53]-[i95]... 

Kaminsky [92] was the first to report a method in which the filler surfaces were treated with metallocene-based catalyst for the production of filled polyolefins. In this method, at first under inert atmosphere, the clay surface is treated with an alkylaluminum compound to reduce the residual water content. In the second step, the catalyst or cocatalyst solution is impregnated onto the clay surface followed by washing with an anhydrous solvent to avoid excess catalyst leaching from the support during the polymerization. Additional alkylaluminum compounds may be used during the course of polymerization. This polymerization-filling technique is a widely used procedure for the synthesis of polymer/clay nanocomposites using coordination catalysts [60, 93, 94]. 

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