Photoisomerization-induced tunable LCST phase separation of azobenzene-containing polymers in an ionic liquid

4-Phenylazophenyl methacrylate (AzoMA) and benzyl methacrylate (BnMA) were copolymerized to produce multistimuli-responsive polymers (P(AzoMA-r-BnMA)s) in a hydrophobic ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([C2mim][NTf2]), as the solvent. P(AzoMA-r-BnMA)s with a maximum of ca. 4 mol % AzoMA were soluble in [C2mim][NTf2] at low temperatures, and they underwent lower critical solution temperature (LCST) phase separation with an increase in temperature. Under UV and visible light irradiation, P(AzoMA-r-BnMA)s underwent reversible photochromism of trans-to-cis and cis-to-trans isomerization, respectively. The LCST temperature differences between trans- and cis-form polymers in the IL were as large as 22 °C. Reversible photoinduced phase separation of the polymers was achieved at a certain temperature; at this temperature, the cis-form polymers were soluble in the IL, but the trans-form polymers were not.