Computational and Experimental Evaluation of Peroxide Oxidants for Amine-Peroxide Redox Polymerization

Journal Article · Fri Nov 13 04:00:00 EST 2020 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.0c02069· OSTI ID:1770899

Musgrave III, Charles B.; Kim, Kangmin; Singstock, Nicholas R.; Salazar, Austyn M.; Stansbury, Jeffrey W.; Musgrave, Charles B.

Amine–peroxide redox polymerization (APRP) is the prevalent method for producing radical-based polymers in the many industrial and medical applications where light or heat activation is impractical. We recently developed a detailed description of the APRP initiation process through a combined computational and experimental effort to show that APRP proceeds through SN2 attack by the amine on the peroxide, followed by the rate-determining homolysis of the resulting intermediate. Using this new mechanistic understanding, a variety of peroxides were computationally predicted to initiate APRP with fast kinetics. In particular, the rate of APRP initiation can be improved by radical and anion stabilization through increased p-electron conjugation or by increasing the electrophilicity of the peroxy bond through the addition of electron-withdrawing groups. On the other hand, the addition of electron-donating groups lowered the initiation rate. These design principles enabled the computational prediction of several new peroxides that exhibited improved initiation rates over the commonly used benzoyl peroxide. For example, the addition of nitro groups (NO2) to the para positions of benzoyl peroxide resulted in a theoretical radical generation rate of 1.9 × 10–9 s–1, which is ~150 times faster than the 1.3 × 10–11 s–1 radical generation rate observed with unsubstituted benzoyl peroxide. These accelerated kinetics enabled the development of a redox-based direct-writing process that exploited the extremely rapid reactivity of an optimized redox pair with a custom inkjet printer, capable of printing custom shapes from polymerizing resins without heat or light. Furthermore, the application of more rapid APRP kinetics could enable the acceleration of existing industrial processes, make new industrial manufacturing methods possible, and improve APRP compatibility with biomedical applications through reduced initiator concentrations that still produce rapid polymerization rates.

• Research Organization: National Renewable Energy Laboratory (NREL), Golden, CO (United States)
• Sponsoring Organization: USDOE Office of Energy Efficiency and Renewable Energy (EERE)
• DOE Contract Number: AC36-08GO28308
• OSTI ID: 1770899
• Report Number(s): NREL/JA-5K00-79402; MainId:33628; UUID:6b812eca-bed9-40d9-84ee-273003ae4046; MainAdminID:19929
• Journal Information: Macromolecules, Journal Name: Macromolecules Journal Issue: 22 Vol. 53
• Country of Publication: United States
• Language: English

Related Subjects

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
functional polymers
kinetics
medical applications
oxidation
polymerization