File(s) not publicly available
RAFT synthesis of branched acrylic copolymers
journal contribution
posted on 2023-06-08, 00:33 authored by Cong-Duan Vo, J Rosselgong, Steven P Armes, Norman C BillinghamWe report the synthesis of branched acrylic copolymers based on 2-hydroxypropyl acrylate using reversible addition fragmentation chain transfer (RAFT) polymerization in tert-butanol at 80 °C. Three branching comonomers were investigated in this study:? ethylene glycol diacrylate, bisphenol A ethoxylated diacrylate and a disulfide-based diacrylate. The latter comonomer allows chemical degradation of the branched acrylic copolymers to produce thiol-functionalized primary chains. Gel permeation chromatography analysis of these degraded copolymer chains indicated low polydispersities (Mw/Mn < 1.22), which confirmed that the living character of the RAFT chemistry was retained under branching conditions. RAFT allows significantly more than one branching agent per primary chain to be used in the copolymerization without causing gelation. This result was obtained with all three branching comonomers and differs from the near-ideal copolymerizations previously reported for the ATRP synthesis of branched methacrylic copolymers (Macromolecules 2006, 39, 7483-7492). Detailed HPLC analysis of the RAFT copolymerization of 2-hydroxypropyl acrylate with bisphenol A ethoxylated diacrylate indicates near-statistical incorporation of the latter comonomer. We suggest that intramolecular cyclization is the primary reason for the apparent violation of classical Flory-Stockmayer gelation theory. This hypothesis is supported by the observation that substantially more ethylene glycol diacrylate than bisphenol A ethoxylated diacrylate can be tolerated in such branching copolymerizations without causing gelation.
History
Publication status
- Published
Journal
MacromoleculesExternal DOI
Volume
40Page range
7119-7125Department affiliated with
- Chemistry Publications
Full text available
- No
Peer reviewed?
- Yes
Legacy Posted Date
2012-02-06Usage metrics
Categories
No categories selectedKeywords
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC