New Polymer Structures Based on Vinyl Ether Polymerization

Sequential living cationic polymerization of octadecyl vinyl ether (ODVE) and methyl vinyl ether (MVE) was used for the preparation of amphiphilic ABA-type block copolymers. The polymerization of ODVE was initiated with the trimethyl silyl iodide/1,1,3,3-tetramethoxy propane/ZnI2 system at 0°C in toluene. The living bifunctional polyODVE thus obtained was used as initiator for the polymerization of MVE. Below the LCST of polyMVE (37°C), the copolymers are amphiphiles. Above the LCST of polyMVE, the polyMVE-blocks become hydrophobic and the amphiphilic nature of the block copolymer is lost. This was demonstrated by using the block copolymers as emulsifiers for water/decane mixtures. The emulsions were stable for several hours at room temperature, while the emulsion stability decreased to about 30 seconds at 40°C. PolyMVE-α,ω-bis-methacrylates were obtained by end-capping of living bifunctional polyMVE with 2-hydroxyethyl methacrylate (HEMA). Copolymerization of these bis-macromers with HEMA leads to segmented networks. The networks showed a reversible swelling/deswelling behavior in water as a function of temperature. This is caused by a change of the hydrophilicity of the polyMVE segments in the networks. Hexa(chloromethyl)melamine, combined with zinc chloride was found to be an efficient hexafunctional initiator for the living cationic polymerization of vinyl ethers. This simple initiating system opens new ways for the synthesis of endgroup-functionalized star-shaped poly(vinyl ethers).