Synthesis and properties of poly(2-adamantyl vinyl ether)-based optical plastics

Cationic polymerization of 2-adamantyl vinyl ether (2-vinyloxytricyclo[3.3.1.13,7]decane; 2-AdVE) and copolymerization of 2-AdVE with n-butyl vinyl ether (NBVE), 2-methoxyethyl vinyl ether (MOVE), or 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA), vinyl ethers containing a flexible chain or a polymerizable group, were performed to obtain poly(vinyl ether) plastics for optical use. With the living cationic initiating systems such as isobutyl vinyl ether–acetic acid adduct/ethylaluminum sesquichloride (IBEA/Et1.5AlCl1.5) or the hydrogen chloride/zinc chloride (HCl/ZnCl2), all the obtained copolymers had unimodal and relatively narrow molecular weight distributions (polydispersity ratio: Mw/Mn = ~1.5 at high conversion) throughout the copolymerizations. These results indicate that the copolymerizations of 2-AdVE with the three comonomers led to the statistical copolymers without contamination of homopolymers. With BF3OEt2 as an initiator, homopolymer of 2-AdVE and poly(2-AdVE)-based polymers, poly(2-AdVE-stat-NBVE), poly(2-AdVE-stat-MOVE), and poly(2-AdVE-stat-VEEA), were produced with high-molecular weights (Mn = 31,800–116,000) in toluene at −30 °C in quantitative yield within 10 min. They have excellent thermal stability owing to their high glass transition and thermal decomposition temperatures. The transparency (86–91 %) and refractive index (1.52–1.53) of the molded polymers are similar to those of conventional optical plastics such as poly(methyl methacrylate) (PMMA) and polycarbonate (PC), whereas their specific gravity (1.09–1.12) and water absorption (0.06–0.17 %) are significantly lower than those of PMMA and PC. In addition, the Abbe number of poly(2-AdVE), poly(2-AdVE-stat-NBVE), and poly(2-AdVE-stat-MOVE) exceeded 60 and was higher than those of PMMA and PC, indicating that the poly(2-AdVE)-based plastics are very suitable for optical lens.