TAILIEUCHUNG - Chapter 7: Dimerization, oligomerization and polymerization of alkenes and alkynes

The annual production of various polymers can be measured only in billion tons of which polyolefins alone figure around 100 million tons per year. In addition to radical and ionic polymerization, a large part of this huge amount is manufactured by coordination polymerization technology. The most important Ziegler-Natta, chromium- and metallocene-based catalysts, however, contain early transition metals which are too oxophilic to be used in aqueous media. Nevertheless, with the late transition metals there is some room for coordination polymerization in aqueous systems [1,2] and the number of studies published on this topic is steadily growing. . | Chapter 7 Dimerization oligomerization and polymerization of alkenes and alkynes The annual production of various polymers can be measured only in billion tons of which polyolefins alone figure around 100 million tons per year. In addition to radical and ionic polymerization a large part of this huge amount is manufactured by coordination polymerization technology. The most important Ziegler-Natta chromium- and metallocene-based catalysts however contain early transition metals which are too oxophilic to be used in aqueous media. Nevertheless with the late transition metals there is some room for coordination polymerization in aqueous systems 1 2 and the number of studies published on this topic is steadily growing. Dimerization and polymerization of ethylene Coordination polymerization of ethylene by late transition metals is a rather slow process especially when the catalyst is dissolved in water. In a study of the interaction of CH2 CH2 and Ru H2O 6 tos 2 tos tosylate both Ru CH2 CH2 H2O 5 tos 2 and Ru CH2 CH2 2 H2O 4 tos 2 were isolated by evaporation of the aqueous phase which had been previously pressurized with 60 bar ethylene at room temperature for 6 and 18 hours respectively. Longer reaction times 72 h led to the formation of butenes with no further oligomerization. This aqueous catalytic dimerization was not selective the product mixture contained Z-2-butene E-2-butene and 1-butene in a 1 ratio 3 . The facially coordinating l 4 7-trimethyl-l 4 7-triazacyclononane Cn ligand forms stable methylrhodium III complexes such as Rh Me 3Cn Rh Me 2Cn OTf and Rh Me Cn OTf 2 OTf trifluoromethanesulfonate and the latter two have rich aqueous chemistry. When dissolved in water Rh Me Cn 2 readily coordinates two water molecules to form the 237 238 Chapter 7 octahedral Rh Me H2O 2Cn 2 in which the aqua ligands undergo sequential deprotonation in basic solutions with pKa i and pKa 2 Scheme 4 . Rh MeXOHXH O Cn . . n CH2 CH --------------- f-CH CH

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