Stimuli-responsive polymers functionalized with reactive inorganic groups enable creation of macromolecular structures such as hydrogels, micelles, and coatings that demonstrate smart behavior. Prior studies using poly( N -isopropyl acrylamide- co -3-(trimethoxysilyl)propyl methacrylate) (P(NIPAM- co -TMA)) have stabilized micelles and produced functional nanoscale coatings; however, such systems show limited responsiveness over multiple thermal cycles. Here, polymer architecture and TMA content are connected to the aqueous self-assembly, optical response, and thermoreversibility of two distinct types of PNIPAM/TMA copolymers: random P(NIPAM- co -TMA), and a ‘blocky-functionalized’ copolymer where TMA is localized to one portion of the chain, P(NIPAM- b -NIPAM- co -TMA). Aqueous solution behavior characterized via cloud point testing (CPT), dynamic light scattering (DLS), and variable-temperature nuclear magnetic resonance spectroscopy (NMR) demonstrates that thermoresponsiveness and thermoreversibility over multiple cycles is a strong function of polymer configuration and TMA content. Despite low TMA content (≤2 mol%), blocky-functionalized copolymers assemble into small, well-ordered structures above the cloud point that lead to distinct transmittance behaviors and stimuli-responsiveness over multiple cycles. Conversely, random copolymers form disordered aggregates at elevated temperatures, and only exhibit thermoreversibility at negligible TMA fractions (0.5 mol%); higher TMA content leads to irreversible structure formation. This understanding of the architectural and assembly effects on the thermal cyclability of aqueous PNIPAM- co -TMA can be used to improve the scalability of responsive polymer applications requiring thermoreversible behavior, including sensing, separations, and functional coatings.
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Blocky bromination of syndiotactic polystyrene via post-polymerization functionalization in the heterogeneous gel state
This work demonstrates the successful blocky bromination of syndiotactic polystyrene (sPS- co -sPS-Br) copolymers containing 6–30 mol% p -bromostyrene units, using a post-polymerization functionalization method conducted in the heterogeneous gel state. For comparison, a matched set of randomly brominated sPS- co -sPS-Br copolymers was prepared using homogeneous (solution-state) reaction conditions. The degree of bromination and copolymer microstructure were evaluated using 1 H and 13 C nuclear magnetic resonance (NMR) spectroscopy. The NMR spectra of gel-state (Blocky) and solution-state (Random) copolymers exhibit strikingly different resonance frequencies and peak intensities above 6 mol% Br and provide direct evidence that functionalization in the gel state produces copolymers with non-random “blocky” microstructures. Quenched films of the Blocky copolymers, analyzed using ultra-small-angle X-ray scattering (USAXS) and small-angle X-ray scattering (SAXS), show micro-phase separated morphologies, which further supports that the Blocky copolymers contain distinct segments of pure sPS and segments of randomly brominated sPS unlike their completely Random analogs. Crystallization behavior of the copolymers, examined using differential scanning calorimetry (DSC), demonstrates that the Blocky copolymers are more crystallizable and crystallize faster at lower supercooling compared to their Random analogs. Computer simulations of the blocky copolymers were developed based on the semicrystalline morphology of a 10 w/v% sPS/CCl 4 gel, to rationalize the effect of heterogeneous functionalization on copolymer microstructure and crystallization behavior. The simulations were found to agree with the microstructural analysis based on the NMR results and confirm that restricting the accessibility of the brominating reagent to monomers well removed from the crystalline fraction of the gel network produces copolymers with a greater prevalence of long, uninterrupted sPS homopolymer sequences. Thus, the blocky microstructure is advantageous for preserving desired crystallizability of the resulting blocky copolymers.
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- Award ID(s):
- 1809291
- PAR ID:
- 10092150
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 9
- Issue:
- 41
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 5095 to 5106
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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