Radical polymerization is undoubtedly the most convenient method to synthesize polymers. Because of the ease of the process, more than 50% of all plastics have been produced industrially in this way. RDRP allows synthetizing precisely controlled polymers while retaining the advantages of free radical polymerization. However, the currently available techniques are mostly limited to the more reactive monomers and it is of interest to find efficient methods to prepare controlled polymers of less reactive monomers such as fluoroolefins. The higher reactivity of the associated radicals leads to stronger bonds with the moderating agent and inefficient reactivation of the dormant species. Organometallic mediated radical polymerization (OMRP) is a recent RDRP technique based on reversible trapping of the radical chain by a metal complex, to form a thermally labile metal-carbon bond in the dormant species. By choosing the appropriate metal and by ligand engineering it should be possible to labilize bonds to strong radicals. We present the synthesis and full characterization of several new alkyl and fluorinated alkyl manganese pentacarbonyl complexes, R-Mn(CO)5 (e.g. R = -CH2CF3, -CF2CH3, -CHMeOCOCH3), of interest as OMRP initiators and dormant chains models for fluorinated and non-fluorinated polymers. The synthesis and characterizations of these complexes will be detailed and the first polymerization results will be shown and discussed. Furthermore, experimental investigations and theoretical calculations of the (CO)5Mn-R bond-dissociation energies will also be presented.

Synthesis and characterization of alkyl and fluorinated alkyl manganese pentacarbonyl complexes as models for reversible-deactivation radical polymerization (RDRP)

254th National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.