Nonlinear optically active polymethacrylates with high glass transition temperatures

Abstract

AbstractA number of novel nonlinear optically (NLO) active polymethacrylates were prepared from the NLO active methacrylates 2a–d with azobenzene side groups and the bulky comonomer 1‐adamantyl methacrylate. The polymers exhibit unusually high glass transition temperatures between 160°C and 190°C. The copolymerization parameters of the monomer pair 1‐adamantyl methacrylate (1)/Disperse red methacrylate 2b (r1 = 1,1 ± 0,2, r2 = 0,8 ± 0,2) show that the two monomers are incorporated almost statistically into the polymer chain. Polymers 3a–d are soluble in common organic solvents and excellent films can be obtained by spin coating. After poling in an electric field of 120 V/μm polymer 3b shows a large electrooptic (EO) coefficient (r33) of 25 pm/V at 633 nm. Within two weeks, only a negligible decay of 7% of the EO coefficient was observed at room temperature. On‐line monitoring of the second harmonic generation (SHG) at 100°C showed a fast initial drop (10%) of the SHG signal and subsequently a slow decay of 20% within 10 h. Afterwards, the signal remained almost constant for further 5 h at 100°C. The novel polymers can thus be considered as easy processible NLO materials with a high thermal stability of the chromophore orientation obtained by poling.