Article: “One-Pot” Aminolysis/Thiol–Maleimide End-Group Functionalization of RAFT Polymers: Identifying and Preventing Michael Addition Side Reactions
Macromolecules. 2016 Sept. 13, v. 49, no. 17
2016
Abstract: ... catalyzed Michael reactions of the representative thiol ethyl 2-mercaptopropionate (E2MP) and NMM in polar ...
Abstract | We show that many of the nucleophiles (catalysts, reducing agents, amines, thiols) present during “one-pot” aminolysis/thiol–maleimide end-group functionalization of RAFT polymers can promote side reactions that substantially reduce polymer end-group functionalization efficiencies. The nucleophilic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene and the reducing agent tributylphosphine were shown to initiate anionic polymerization of N-methylmaleimide (NMM) in both polar and nonpolar solvents whereas hexylamine-initiated polymerization of NMM occurred only in high-polarity solvents. Furthermore, triethylamine-catalyzed Michael reactions of the representative thiol ethyl 2-mercaptopropionate (E2MP) and NMM in polar solvents resulted in anionic maleimide polymerization when [NMM]0 > [E2MP]0. Base-catalyzed enolate formation on the α-carbon of thiol–maleimide adducts was also shown as an alternative initiation pathway for maleimide polymerization in polar solvents. Ultimately, optimal “one-pot” reaction conditions were identified allowing for up to 99% maleimide end-group functionalization of dithiobenzoate-terminated poly(N,N-dimethylacrylamide). Much of the work described herein can also be used to ensure near-quantitative conversion of small molecule thiol–maleimide reactions while preventing previously unforeseen side reactions. |
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Keywords | amines ; catalysts ; Lewis bases ; polymerization ; polymers ; reducing agents ; solvents ; thiols |
Language | English |
Dates of publication | 2016-0913 |
Size | p. 6193-6202. |
Publishing place | American Chemical Society |
Document type | Article |
ZDB-ID | 1491942-4 |
ISSN | 1520-5835 ; 0024-9297 |
ISSN (online) | 1520-5835 |
ISSN | 0024-9297 |
DOI | 10.1021%2Facs.macromol.6b01512 |
Database | NAL-Catalogue (AGRICOLA) |
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