화학공학소재연구정보센터
Macromolecules, Vol.50, No.4, 1482-1493, 2017
Preparation and Cross-Linking of All-Acrylamide Diblock Copolymer Nano-Objects via Polymerization-Induced Self-Assembly in Aqueous Solution
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 degrees 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 degrees 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 degrees 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.