期刊
POLYMER CHEMISTRY
卷 6, 期 3, 页码 436-447出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4py01238k
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资金
- Australian Research Council (ARC) [DE120101547]
- Australian Research Council [DE120101547] Funding Source: Australian Research Council
A novel class of thiol-reactive (meth)acrylate monomers and the quantitative postpolymerization modification of their RAFT-made (co)polymers with aromatic, glycosidic, and aliphatic thiols are presented. A set of 6 different N-functional 2-(meth)acryloyloxy-2-(pentafluorophenyl) acetamide monomers bearing pentafluorophenyl groups was prepared by a Passerini three-component reaction of (meth)acrylic acid, 2,3,4,5,6-pentafluorobenzaldehyde, and various isocyanides in water in up to near-quantitative isolated yields. RAFT polymerization was used to produce well-defined homopolymers and copolymers with methyl methacrylate, tert-butyl methacrylate, poly(ethylene glycol) methyl ether (meth)acrylate, and pentafluorophenyl acrylate, with low polydispersity indices of generally D-M <= 1.23. In the presence of base, (co)polymers underwent selective para-fluoro substitution reactions with thiols in the absence of any side reactions observable by H-1 and F-19 NMR spectroscopy and size exclusion chromatography. The selection of employed thiols included various alkanethiols, a thiolated glucose derivative, mercaptopropionic acid, L-cysteine and the drug captopril. F-19 NMR kinetic measurements indicated quantitative thiol-para-fluoro substitutions after <3-80 min at 25-45 degrees C using 1-1.1 equiv. of thiol, depending on the reactivity of the employed thiol (aromatic, glycosidic > primary aliphatic > secondary aliphatic > tertiary aliphatic) and the choice of a suitable base (triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)). The versatility of thiol-reactive (meth)acrylate species is demonstrated by the examples of a thermoresponsive copolymer showing a thiol-sensitive lower critical solution temperature (LCST) and the selective sequential modification with thiols and amines of a doubly reactive copolymer containing activated pentafluorophenyl esters.
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