High stability poly(N-adamantyl-exo-norbornene-5,6-dicarboximide) and phenyl vinylene thiophene electro-optic host-guest system

[Display omitted] •Well controlled poly(N-adamantyl-exo-norbornene-5,6-dicarboximide) was prepared by ring opening metathesis polymerization.•Host/guest blends were prepared using Poly(ADNDI) as the host and high polarizability FTC chromophores as the guests.•Chromophores with a large and bulky side group performed much better than those with aromatic, hydrophilic or no side group.•Temporal and thermal stabilities of the blends were evaluated and compared to a commercially available high Tg polymer.•A high EO coefficient and a high stability system was developed. Poly(N-adamantyl-exo-norbornene-5,6-dicarboximide) was prepared by ring opening metathesis polymerization. This was achieved in chloroform using the Grubbs 1st generation initiator and quenched with ethyl vinyl ether. The polymer had a weight average molecular weight of 27,000g/mol with a polydispersity index of 2.19, a high glass transition temperature of 281°C and a high thermal decomposition temperature of 385°C (10% loss). The trans:cis vinylene ratio was 1.00:0.19 making the polymer amorphous. The polymer was used as a host for 5 guest nonlinear optical chromophores. The relationship between the chromophore structure and the electro-optic coefficient was investigated. A range of chromophore concentrations were evaluated and it was found that the ideal chromophore structure included a bulky tert-butyldiphenylsilane side group. A maximum r33 of 80pm/V was obtained at a chromophore concentration of 45wt% and a poling temperature of 160°C. A host-guest system containing 35wt% of the tert-butyldiphenylsilane substituted chromophore had a stability of 85% at a temperature of 85°C for 500h. The stability at 105°C was 72%. In comparison amorphous polycarbonate under the same conditions achieved a stability of just 58% at 85°C, while poly(methyl methacrylate) had a stability of 0% at 85°C.