Open AccessPreparation and Cross-Linking of All-Acrylamide Diblock Copolymer Nano-Objects via Polymerization-Induced Self-Assembly in Aqueous Solution
Author(s) -
Sarah J. Byard,
Mark Williams,
Beulah E. McKenzie,
Adam Blanazs,
Steven P. Armes
Publication year - 2017
Publication title -
macromolecules
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.994
H-Index - 313
eISSN - 1520-5835
pISSN - 0024-9297
DOI - 10.1021/acs.macromol.6b02643
Subject(s) - copolymer , polymer chemistry , polymerization , dynamic light scattering , chain transfer , aqueous solution , dispersion polymerization , degree of polymerization , raft , vesicle , chemical engineering , materials science , chemistry , nanoparticle , radical polymerization , polymer , organic chemistry , nanotechnology , membrane , biochemistry , engineering
Various carboxylic acid-functionalized poly( N , N -dimethylacrylamide) (PDMAC) macromolecular chain transfer agents (macro-CTAs) were chain-extended with diacetone acrylamide (DAAM) by reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization at 70 °C and 20% w/w solids to produce a series of PDMAC-PDAAM diblock copolymer nano-objects via polymerization-induced self-assembly (PISA). TEM studies indicate that a PDMAC macro-CTA with a mean degree of polymerization (DP) of 68 or higher results in the formation of well-defined spherical nanoparticles with mean diameters ranging from 40 to 150 nm. In contrast, either highly anisotropic worms or polydisperse vesicles are formed when relatively short macro-CTAs (DP = 40-58) are used. A phase diagram was constructed to enable accurate targeting of pure copolymer morphologies. Dynamic light scattering (DLS) and aqueous electrophoresis studies indicated that in most cases these PDMAC-PDAAM nano-objects are surprisingly resistant to changes in either solution pH or temperature. However, PDMAC 40 -PDAAM 99 worms do undergo partial dissociation to form a mixture of relatively short worms and spheres on adjusting the solution pH from pH 2-3 to around pH 9 at 20 °C. Moreover, a change in copolymer morphology from worms to a mixture of short worms and vesicles was observed by DLS and TEM on heating this worm dispersion to 50 °C. Postpolymerization cross-linking of concentrated aqueous dispersions of PDMAC-PDAAM spheres, worms, or vesicles was performed at ambient temperature using adipic acid dihydrazide (ADH), which reacts with the hydrophobic ketone-functionalized PDAAM chains. The formation of hydrazone groups was monitored by FT-IR spectroscopy and afforded covalently stabilized nano-objects that remained intact on exposure to methanol, which is a good solvent for both blocks. Rheological studies indicated that the cross-linked worms formed a stronger gel compared to linear precursor worms.