Synthesis and Functionalization of Cross-Linking Macroinimers for Photocurable Systems

Luis L. Jessen; Tanner L. Grover; Dean Afsar; Erion Hasa; Patricia R. Calvo; C. Allan Guymon

doi:10.1021/acsapm.5c02714

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Synthesis and Functionalization of Cross-Linking Macroinimers for Photocurable Systems

Journal article

Peer reviewed

Synthesis and Functionalization of Cross-Linking Macroinimers for Photocurable Systems

Luis L. Jessen, Tanner L. Grover, Dean Afsar, Erion Hasa, Patricia R. Calvo and C. Allan Guymon

ACS applied polymer materials, Vol.7(19), pp.13247-13255

09/30/2025

DOI: 10.1021/acsapm.5c02714

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Abstract

Hyperbranched prepolymers (HBPs) bearing acrylate functionalities were functionalized via photoiniferter RAFT (PI-RAFT) block copolymerization using multifunctional acrylates. By controlling the reagent functional group concentrations, the oligomer size was controlled, while pendant double bonds were efficiently added over short time periods. Throughout the reaction, three competing pathways, namely, functionalization, internal cyclization, and combination, were identified along with their dependence on HBP size. The ability to simultaneously initiate and cross-link photopolymer networks was subsequently investigated by placing functionalized HBPs in the presence of a monofunctional reactive diluent. Additionally, 3D-printed structures were formed using HBPs as cross-linking agents, resulting in the formation of elastomeric structures. This study demonstrates that acrylate-functional oligomers can be designed and synthesized using facile and rapid PI-RAFT copolymerization and subsequently used to both cross-link and initiate photopolymer materials.

photopolymerization

RAFTpolymerization

3Dprinting

hyperbranched polymers

isocyanate-free

backbone functionalization

Details

Title: Subtitle: Synthesis and Functionalization of Cross-Linking Macroinimers for Photocurable Systems
Creators: Luis L. Jessen - University of Iowa
Tanner L. Grover
Dean Afsar - Kansas State University
Erion Hasa - Stratasys
Patricia R. Calvo - Kansas State University
C. Allan Guymon - Brigham Young University
Resource Type: Journal article
Publication Details: ACS applied polymer materials, Vol.7(19), pp.13247-13255
DOI: 10.1021/acsapm.5c02714
ISSN: 2637-6105
eISSN: 2637-6105
Publisher: American Chemical Society
Grant note: Industry/University Cooperative Research Center for Fundamentals and Applications of PhotopolymerizationIndustry/University Cooperative Research Center (I/UCRC) for Fundamentals and Applications of Photopolymerization
Financial support for this work was provided by the Industry/University Cooperative Research Center (I/UCRC) for Fundamentals and Applications of Photopolymerization.
Language: English
Date published: 09/30/2025
Academic Unit: Chemical and Biochemical Engineering
Record Identifier: 9984968459002771

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