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PreprintCC BYChemRxiv

On the Mechanism of Catalytic Chain Transfer Photopolymerization (CCTP2): the Good, the Bad and the Ugly

  • Nicholas R. Bagnall1,2
  • Meredith H. Jones1,2
  • Talon M. Kosak1,2
  • Brian R. Donovan1,2
  • Abdulaziz W. Alherz3,4
  • Brady T. Worrell1,2
4 affiliations
  1. 1Department of Chemistry & Biochemistry
  2. 2University of Denver
  3. 3Department of Chemical Engineering, College of Engineering & Petroleum
  4. 4Sabah Al Salem University City
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Abstract

Previously, the addition of catalytic quantities of cobalt(II) complexes to standard methacrylatebased formulations was found to reduce the crosslinking density, glass transition temperature, modulus and stiffness of the resultant photopolymeric materials proportional to catalyst loading. We have dubbed this technique catalytic chain transfer photopolymerization (CCTP2), which is conceptually and mechanistically linked to its predecessor catalytic chain transfer polymerization (CCTP), but uses photoinitiation, multifunctional methacrylate monomers, and creates crosslinked 2 materials. Expansion of this technology has been met with issues related to non-linear catalyst performance, limited methacrylate conversion, and long exposure times. These roadblocks prompted us to develop a working mechanistic model for CCTP2 using a combined experimental and computational approach, which is presented here. We anticipate that understanding the good, the bad, and the ugly of this catalytic process will inform future catalyst development, formulation chemistry, and broader applications of this technique towards the synthesis of functional materials and stereolithography.

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Cite

BibTeXRIS
BibTeX
@misc{bagnall2026mechanism,
  title = {{On the Mechanism of Catalytic Chain Transfer Photopolymerization (CCTP2): the Good, the Bad and the Ugly}},
  author = {Nicholas R. Bagnall and Meredith H. Jones and Talon M. Kosak and Brian R. Donovan and Abdulaziz W. Alherz and Brady T. Worrell},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010029/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010029/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - On the Mechanism of Catalytic Chain Transfer Photopolymerization (CCTP2): the Good, the Bad and the Ugly
AU  - Nicholas R. Bagnall
AU  - Meredith H. Jones
AU  - Talon M. Kosak
AU  - Brian R. Donovan
AU  - Abdulaziz W. Alherz
AU  - Brady T. Worrell
PY  - 2026
DA  - 2026/10/07
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010029/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010029/v1
AB  - Previously, the addition of catalytic quantities of cobalt(II) complexes to standard methacrylatebased formulations was found to reduce the crosslinking density, glass transition temperature, modulus and stiffness of the resultant photopolymeric materials proportional to catalyst loading. We have dubbed this technique catalytic chain transfer photopolymerization (CCTP2), which is conceptually and mechanistically linked to its predecessor catalytic chain transfer polymerization (CCTP), but uses photoinitiation, multifunctional methacrylate monomers, and creates crosslinked 2 materials. Expansion of this technology has been met with issues related to non-linear catalyst performance, limited methacrylate conversion, and long exposure times. These roadblocks prompted us to develop a working mechanistic model for CCTP2 using a combined experimental and computational approach, which is presented here. We anticipate that understanding the good, the bad, and the ugly of this catalytic process will inform future catalyst development, formulation chemistry, and broader applications of this technique towards the synthesis of functional materials and stereolithography.
ER  -