SUMMARY: New polymer networks were prepared by free radical initiated copolymerization of crystallizable a,x-bismethacrylate-terminated poly(octadecyl vinyl ether) (polyODVE) with butyl acrylate (BA). The polyODVE bismacromonomers were obtained by end-capping the bifunctionally living cationic polymerization of ODVE with 2-hydroxyethyl methacrylate (HEMA). The segmented networks show a high degree of phase separation over a wide range of compositions. The shape memory properties of a material containing 20 wt.-% of polyODVE are reported.

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A semi-continuous process for the controlled cationic polymerization of methyl vinyl ether (MVE) was developed. The initiating system was a combination of 1,1-diethoxyethane(DEE), trimethyl silyl iodide (TMSI), and ZnI 2 as activator. The optimal reaction conditions were a reaction temperature of ¡5 ± C in toluene, an initiator to activator ratio of 5 to 1, and a monomer feed rate of 0.86 mol/ h. With these reaction conditions, poly(methyl vinyl ethers) (PMVEs) with molecular weights up to 7500 could be prepared in quantities up to 30 g with narrow molecular weight distributions (MWD 1.2) and still possessing active chain ends which can be end-capped with a nucleophilic terminator.

The living cationic polymerization of vinyl ethers has been used to prepare a number of new polymers with special properties. Sequential polymerization of the hydrophilic methyl vinyl ether (MVE) and the hydrophobic octadecyl vinyl ether (ODVE) has lead to amphiphilic block‐copolymers with emulsifying properties for water/decane mixtures. Poly(vinyl‐ether) macromonomers were obtained by end‐capping of living polymers with hydroxyethyl acrylate. Copolymerization of polyODVE‐macromonomer with usual acrylates lead to highly branched hydrophobic polymers. When the end‐capping was performed with bifunctionally living polymers, the corresponding “bis‐macromonomers” were obtained. Copolymerization of such bis‐macromonomers with styrene or butyl acrylate, leads to the formation of segmented polymer networks. In the case of polyODVE‐poly(butyl acrylate), these networks showed a pronounced phase separation. Due to the crystallinity of the polyODVE domains, these materials showed shape memory properties.

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