Cosolvent incorporation modulates the thermal and structural response of PNIPAM/silyl methacrylate copolymers

Polymers functionalized with inorganic silane groups have been used in wide-ranging applications due to the silane reactivity, which enables formation of covalently-crosslinked polymeric structures. Utilizing stimuli-responsive polymers in these hybrid systems can lead to smart and tunable behavior for sensing, drug delivery, and optical coatings. Previously, the thermoresponsive polymer poly(N-isopropyl acrylamide) (PNIPAM) functionalized with 3-(trimethoxysilyl)propyl methacrylate (TMA) demonstrated unique aqueous self-assembly and optical responses following temperature elevation. Here, we investigate how cosolvent addition, particularly ethanol and N,N-dimethyl formamide (DMF), impacts these transition temperatures, optical clouding, and structure formation in NIPAM/TMA copolymers. Versus purely aqueous systems, these solvent mixtures can introduce additional phase transitions and can alter the two-phase region boundaries based on temperature and solvent composition. Interestingly, TMA incorporation strongly alters phase boundaries in the water-rich regime for DMF-containing systems but not for ethanol-containing systems. Cosolvent species and content also alter the aggregation and assembly of NIPAM/TMA copolymers, but these effects depend on polymer architecture. For example, localizing the TMA towards one chain end in 'blocky' domains leads to formation of uniform micelles with narrow dispersities above the cloud point for certain solvent compositions. In contrast, polydisperse aggregates form in random copolymer and PNIPAM homopolymer solutions - the size of which depends on solvent composition. The resulting optical responses and thermoreversibility also depend strongly on cosolvent content and copolymer architecture. Cosolvent incorporation thus increases the versatility of inorganic-functionalized responsive polymers for diverse applications by providing a simple way to tune the structure size and optical response.