Synthesis and characterization of semifluorinated polymers via group transfer polymerization

Group transfer polymerization (GTP) was used to prepare semifluorinated polymers based on acrylic and methacrylic monomers. In the first case, electrophilic catalyzed GTP was applied with 1-methoxy-2-methyl-1-trimethylsilyloxy-1-propene (MMTP) as initiator, zinc iodide as catalyst and 1H,1H,2H,2H-perfluorooctyl acrylate as monomer. In this way it has been possible to obtain oligomers. Higher molecular weight polymers were prepared by means of the nucleophilic tetrabutylammonium benzoate as catalyst. With MMTP as initiator, 1H,1H,2H,2H-perfluoroalkyl methacrylates, F(CF2)(m)(CH2)(2)OCOC(CH3)=CH2, were polymerized to molecular weights > 4.5 kg mol(-1). The polydispersity was found to depend strongly on the length of the perfuoroalkyl side chain, i.e. M-w/M-n decreases with increasing m.