Journal article
Tuning spectral response and polymerization control in nitroxide-mediated photopolymerization (NMP2) initiators via chromophore substitution
Polymer chemistry
07/16/2026
DOI: 10.1039/d6py00374e
Abstract
Three alkoxyamine-based photoinitiators bearing benzophenone (NMP22), naphthol (NMP23), and anthracene (NMP24) chromophores were synthesized to investigate the effect of chromophore identity on spectral response and polymerization control in nitroxide-mediated photopolymerization (NMP2). UV-Vis spectroscopy showed that chromophore selection tuned light absorption across the 200-450 nm range, with the anthracene-based initiator 4 exhibiting the broadest photo-response, extending to 450 nm. Photolysis half-life (t1/2) varied by nearly two orders of magnitude across the series (14 s for 2; 920 s for 3), reflecting chromophore-dependent nitroxide radical stability. All three NMP2 initiators photopolymerized poly(hexyl acrylate) polymers with molecular weights up to nine times greater than a 2,2-dimethoxy-2-phenylacetophenone (DMPA) control and low polydispersity indices, with linear molecular weight growth and pseudo-first-order kinetics confirming controlled, "living" character. Additionally, these NMP2 systems exhibited slower photopolymerization rates than conventional initiators, consistent with the reversible activation-deactivation mechanism inherent to nitroxide-mediated polymerization. This study demonstrates that chromophore substitution provides a practical and tunable route to control radical photopolymerization across a broad range of UV and visible wavelengths.
Details
- Title: Subtitle
- Tuning spectral response and polymerization control in nitroxide-mediated photopolymerization (NMP2) initiators via chromophore substitution
- Creators
- Huayang Fang - University of IowaJennafer M. Davis - Brigham Young UniversityAndrew Chappell - Brigham Young UniversityJon P Scholte - University of IowaC. Allan Guymon - Brigham Young University
- Resource Type
- Journal article
- Publication Details
- Polymer chemistry
- DOI
- 10.1039/d6py00374e
- ISSN
- 1759-9954
- eISSN
- 1759-9962
- Publisher
- Royal Soc Chemistry
- Number of pages
- 14
- Grant note
- University of Colorado Industry/University Cooperative Research Center (IUCRC) for Fundamentals and Applications of Photopolymerization at the University of Iowa, Brigham Young University
- Language
- English
- Electronic publication date
- 07/16/2026
- Academic Unit
- Chemical and Biochemical Engineering
- Record Identifier
- 9985214019802771
Metrics
1 Record Views