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Updated: Jul 13, 2026

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
Published on: February 18, 2022
Functional graft poly(N-isopropyl acrylamide)s using reversible addition-fragmentation chain transfer (RAFT)
Steven R Carter1, Richard M England, Barry J Hunt
1The Polymer and Biomaterials Chemistry Laboratories, Department of Chemistry (Polymer Centre), Brook Hill, University of Sheffield, Sheffield, South Yorkshire, S3 7HF, UK.
Abstract:
A series of NIPAM/4-vinyl benzyl chloride copolymers were substituted with 4(5)-imidazole dithioic acid or N-pyrrole dithioic acid to form multi-functional linear dithioate-functional polymers, which can be used as macromolecular transfer agents in a controlled radical polymerisation (RAFT) process. The presence of imidazole dithioate or N-pyrrole dithioate units along the NIPAM copolymer was determined by (1)H NMR, which showed broad CH-imidazole or CH-N-pyrrole resonances. Subsequent reaction of these multi-branch point polymers to produce graft polymers was achieved by reaction with NIPAM in the presence of AIBN. The graft polymers are produced as mixtures containing the desired product and linear polymer. The linear polymer is produced following transfer to the pendant dithioate group. Some of the branched polymers formed from the imidazole dithioate polymers were insoluble in water whilst others were found to be water soluble only in the presence of copper(II) ions. The use of N-pyrrole dithioate groups was found to substantially increase the solubility of the branched polymers in conventional solvents.
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