Moncada, Adriana I. (2010-05). Metal Catalyzed Formation of Aliphatic Polycarbonates Involving Oxetanes and Carbon Dioxide as Monomers. Doctoral Dissertation.
Thesis
Biodegradable aliphatic polycarbonates are important components of non-toxic thermoplastic elastomers, which have a variety of medical applications. Industrially, aliphatic polycarbonates derived from six-membered cyclic carbonates such as trimethylene carbonate (TMC or 1,3-dioxan-2-one) are produced via ring-opening polymerization (ROP) processes in the presence of a tin catalyst. It is worth mentioning that TMC is readily obtained by transesterification of 1,3-propanediol with various reagents including phosgene and its derivatives. Therefore, it has been of great interest to investigate greener routes for the production of this important class of polymers. Toward this goal, the synthesis of aliphatic polycarbonates via the metal catalyzed alternative coupling of oxetanes and carbon dioxide represents an attractive alternative. The use of an abundant, inexpensive, non-toxic, and biorenewable resource, carbon dioxide, makes this method very valuable. Furthermore, in this reaction, the sixmembered cyclic carbonate byproduct, TMC, can also be ring-opened and transformed into the same polycarbonate. For over a decade, the Darensbourg research group has successfully utilized metal salen complexes as catalysts for the epoxide/CO2 copolymerization process. Hence, this dissertation focuses on the examination of these complexes as catalysts for the oxetane/CO2 copolymerization reaction and the further elucidation of its mechanism. Chromium(III) salen derivatives in the presence of an azide ion initiator were determined to be very effective catalysts for the coupling of oxetanes and carbon dioxide providing polycarbonates with minimal amounts of ether linkages. Kinetic and mechanistic investigations performed on this process suggested that copolymer formation proceeded by two routes. These are the direct enchainment of oxetane and CO2, and the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction. Anion initiators which are good leaving groups, e.g. bromide and iodide, are effective at affording TMC, and hence, more polycarbonate can be formed by the ROP of preformed trimethylene carbonate. Research efforts at tuning the selectivity of the oxetane/CO2 coupling process for TMC and/or polycarbonate produced from the homopolymerization of preformed TMC have been performed using cobalt(II) salen derivatives along with anion initiators. Lastly, investigations of this process involving 3-methoxy-methyl-3-methyloxetane will be presented.
Biodegradable aliphatic polycarbonates are important components of non-toxic thermoplastic elastomers, which have a variety of medical applications. Industrially, aliphatic polycarbonates derived from six-membered cyclic carbonates such as trimethylene carbonate (TMC or 1,3-dioxan-2-one) are produced via ring-opening polymerization (ROP) processes in the presence of a tin catalyst. It is worth mentioning that TMC is readily obtained by transesterification of 1,3-propanediol with various reagents including phosgene and its derivatives. Therefore, it has been of great interest to investigate greener routes for the production of this important class of polymers. Toward this goal, the synthesis of aliphatic polycarbonates via the metal catalyzed alternative coupling of oxetanes and carbon dioxide represents an attractive alternative. The use of an abundant, inexpensive, non-toxic, and biorenewable resource, carbon dioxide, makes this method very valuable. Furthermore, in this reaction, the sixmembered cyclic carbonate byproduct, TMC, can also be ring-opened and transformed into the same polycarbonate. For over a decade, the Darensbourg research group has successfully utilized metal salen complexes as catalysts for the epoxide/CO2 copolymerization process. Hence, this dissertation focuses on the examination of these complexes as catalysts for the oxetane/CO2 copolymerization reaction and the further elucidation of its mechanism. Chromium(III) salen derivatives in the presence of an azide ion initiator were determined to be very effective catalysts for the coupling of oxetanes and carbon dioxide providing polycarbonates with minimal amounts of ether linkages. Kinetic and mechanistic investigations performed on this process suggested that copolymer formation proceeded by two routes. These are the direct enchainment of oxetane and CO2, and the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction. Anion initiators which are good leaving groups, e.g. bromide and iodide, are effective at affording TMC, and hence, more polycarbonate can be formed by the ROP of preformed trimethylene carbonate. Research efforts at tuning the selectivity of the oxetane/CO2 coupling process for TMC and/or polycarbonate produced from the homopolymerization of preformed TMC have been performed using cobalt(II) salen derivatives along with anion initiators. Lastly, investigations of this process involving 3-methoxy-methyl-3-methyloxetane will be presented.
