高分子纳米复合水凝胶光交联过程中的凝胶动力学《ACS Polymers Au》

Gelation Dynamics during Photo-Cross-Linking of Polymer Nanocomposite Hydrogels

Michael C. Burroughs, Tracy H. Schloemer, Daniel N. Congreve, and Danielle J. Mai*

Department of Chemical Engineering, Stanford University, Stanford, California94305, United States

ACS Polym. Au 2022, XXXX, XXX, XXX-XXX

Publication Date: December 5, 2022

https://doi.org/10.1021/acspolymersau.2c00051

Abstract

Embedding nanomaterials into polymer hydrogels enables the design of functional materials with tailored chemical, mechanical, and optical properties. Nanocapsules that protect interior cargo and disperse readily through a polymeric matrix have drawn particular interest for their ability to integrate chemically incompatible systems and to further expand the parameter space for polymer nanocomposite hydrogels. The properties of polymer nanocomposite hydrogels depend on the material composition and processing route, which were explored systematically in this work. The gelation kinetics of network-forming polymer solutions with and without silica-coated nanocapsules bearing polyethylene glycol (PEG) surface ligands were investigated using in situ dynamic rheology measurements. Network-forming polymers comprised either 4-arm or 8-arm star PEG with terminal anthracene groups, which dimerize upon irradiation with ultraviolet (UV) light. The PEG-anthracene solutions exhibited rapid gel formation upon UV exposure (365 nm); gel formation was observed as a crossover from liquid-like to solid-like behavior during in situ small-amplitude oscillatory shear rheology. This crossover time was non-monotonic with polymer concentration. Far below the overlap concentration (c/c* ≪ 1), spatially separated PEG-anthracene molecules were subject to forming intramolecular loops over intermolecular cross-links, thereby slowing the gelation process. Near the polymer overlap concentration (c/c* ∼ 1), rapid gelation was attributed to the ideal proximity of anthracene end groups from neighboring polymer molecules. Above the overlap concentration (c/c* > 1), increased solution viscosities hindered molecular diffusion, thereby reducing the frequency of dimerization reactions. Adding nanocapsules to PEG-anthracene solutions resulted in faster gelation than nanocapsule-free PEG-anthracene solutions with equivalent effective polymer concentrations. The final elastic modulus of nanocomposite hydrogels increased with nanocapsule volume fraction, signifying synergistic mechanical reinforcement by nanocapsules despite not being cross-linked into the polymer network. Overall, these findings quantify the impact of nanocapsule addition on the gelation kinetics and mechanical properties of polymer nanocomposite hydrogels, which are promising materials for applications in optoelectronics, biotechnology, and additive manufacturing.

KEYWORDS:

• Nanocomposite hydrogels

• photo-cross-linking

• rheology

• star polymers

• nanocapsules

• gelation

SUBJECTS:

• Hydrogels,

• Nanocapsules,

• Nanocomposites,

• Polymers,

• Star polymers