Doctoral Dissertations

Date of Award

8-2010

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Jimmy. W. Mays

Committee Members

Durairaj Baskaran, Mark Dadmun, Mike Kilbey, Bin Hu

Abstract

Atom transfer radical polymerization (ATRP) which utilizes transition metal based catalysts is a versatile methodology for the synthesis of a wide spectrum of polymers with controlled architectures. However, high concentrations of soluble catalyst required in an ATRP process makes the final polymer colored and toxic. Thus, the catalyst removal/reduction/recycling remains a challenge in the field of ATRP. Supported catalysts on insoluble solids such as silica gel, polystyrene beads, etc. have been used in ATRP to facilitate the catalyst recovery and recycling. However, the ability of the supported catalysts to mediate a polymerization is substantially reduced due to their reduced mobility and leaching problems. In this thesis, we report a series of novel and recyclable physisorbed CuBr2/N, N, N’, N’’-pentamethyldiethylene-triamine supported catalytic systems operating in conjunction with hydration. Supported aqueous-phase catalysis (SAPC) for ATRP was evaluated for different inorganic (Na-clay, silica and zeolite) and organic (polysaccharides) supports. The hydrated physisorbed supported catalysts were used for the polymerization of benzyl methacrylate and methyl methacrylate using an activator generated electron transfer ATRP process. The catalyst was effectively retained on the surface of supports through hydration as was verified by UV-Vis measurements. The supported catalyst was easily removed from the polymerization by simple filtration process affording a colorless polymer solution. The polymerizations produced high conversion and colorless polymers with moderately narrow polydispersity indices (PDI). The catalyst maintained high activity during the recycling experiments. We also investigated the kinetic and mechanistic behavior of these solid supported polymerization systems. Based on split kinetics experiments and UV-Vis studies it was believed that the activation and deactivation processes took place at the diffused hydrated interface between the solid support and organic phase. The branched (stars and graft) polymers were also synthesized using Na-clay supported catalyst. The produced polymers had narrow PDI and good initiator efficiencies. The functionality of the star polymers was confirmed using 1H NMR and dilute solution properties. The synthesis of graft-copolymer was confirmed by 1H NMR and atomic force microscopy. This thesis demonstrates the successful use of SAPC for ATRP to produce contamination free linear and branched polymers with moderately narrow PDI and high recycling efficiency.

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