Synthesis and properties of water‐soluble azlactone copolymers

Abstract

Preparation and study of a series of copolymers incorporating 2-vinyl-4,4-dimethylazlactone (VDMA) is reported. The reactivity ratios for photo-initiated free radical copolymerization of VDMA with methacrylic acid (MAA), acrylic acid (AA), acrylamide (AAm), dimethylacrylamide (DMAA), hydroxyethyl methacrylate (HEMA), methoxy poly(ethylene glycol) methacrylate (MPEG 300 MA), and 2-methacryloyloxyethyl phosphorylcholine (MPC), were determined by fitting comonomer conversion data obtained by in situ 1 H NMR to a terminal copolymerization equation. Semi-batch photo-copolymerizations were then used to synthesize the corresponding VDMA copolymers with constant composition. Their solubility and dissolution behavior, as well as their hydrolysis half-lives under physiological conditions, were determined. P(VDMA-co-MAA) copolymers with 52 to 93 mol % VDMA showed decreasing initial solubility and increasing hydrolysis half-lives with increasing VDMA content. VDMA copolymers with nonionic monomers AAm and DMAA were water soluble only at VDMA contents of 41 and 22 mol % or less, respectively, and showed longer hydrolysis half-lives than comparable MAA copolymers. VDMA copolymers with HEMA and MPEG 300 MA were found to crosslink during storage, so their hydrolysis half-lives were not determined. VDMA copolymers with 18% zwitterionic MPC showed a much longer half-life and superior initial solubility compared to analogous p(VDMAco-MAA), identifying this copolymer as a promising candidate for macromolecular crosslinkers in, for example, aqueous layerby-layer co-depositions with polyamines. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: [4674][4675][4676][4677][4678][4679][4680][4681][4682][4683][4684][4685] 2012

First investigation of modified poly(2-vinyl-4,4-dimethylazlactone)s as kinetic hydrate inhibitors

“…4) (Gardner et al, 2012). The resemblance of PAMA to the alkylated AMPS polymers described earlier is apparent.…”

Fabrication, chemical modification, and topographical patterning of reactive gels assembled from azlactone‐functionalized polymers and a diamine

“…Azlactone functionality is susceptible to hydrolysis, particularly at high or low pH; however, hydrolysis reactions are typically slower than reactions of azlactones with amines . Furthermore, azlactone groups have been shown to persist for several hours in water when copolymerized with certain water soluble monomers …”

Soft Matter Nanoparticles with Reactive Coronal Pentafluorophenyl Methacrylate Residues via Non-Polar RAFT Dispersion Polymerization and Polymerization-Induced Self-Assembly

“…This includes monomers containing species such as azlactones or pentafluorophenylesters . However, the incorporation of such building blocks (in either the coronal or core structures) would result in the presence of reactive handles that could be used for modification reactions post‐particle formation and thus, in principle, the generation of a large library of novel functional nano‐objects from a single parent nanoparticle precursor …”