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, PDMAC40–PDAAM99 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.

A new amphiphilic diblock copolymer prepared via polymerization-induced self-assembly forms spheres, worms, vesicles or lamellae in aqueous solution on adjusting the temperature.

A range of poly(n-butyl methacrylate-stat-methacrylic acid) [P(BMA-stat-MAA)] statistical copolymers of various compositions and molecular weights ranging from 5 to 30 kDa were prepared using either reversible addition-fragmentation chain transfer (RAFT) solution copolymerization or conventional free radical polymerization in isopropanol (IPA). On dilution with water, these amphiphilic copolymers self-assembled to form spherical nano-objects as confirmed by small-angle X-ray scattering (SAXS) and transmission electron microscopy. Various structural particle models were examined to extract information regarding the mean nano-object size and morphology. It is found that nano-object radii are independent of copolymer molecular weight, but depend on the copolymer composition: the smaller the amount of MAA units in the molecules the larger the nanoobjects are formed. Combined SAXS and aqueous electrophoretic measurements indicated that most of the MAA units are located at the nano-object surface. Furthermore, SAXS and rheology measurements were used to monitor the effect of solvent composition on the copolymer morphology both at a fixed copolymer concentration (either 1 wt% or 25 wt%) and also for a gradual variation in copolymer

For certain commercial applications such as enhanced oil recovery, sterically stabilized colloidal dispersions that exhibit high tolerance toward added salt are desirable. Herein, we report a series of new cationic diblock copolymer nanoparticles that display excellent colloidal stability in concentrated aqueous salt solutions. More specifically, poly-(2-(acryloyloxy)ethyltrimethylammonium chloride) (PATAC) has been chain-extended by reversible addition− fragmentation chain transfer aqueous dispersion polymerization of diacetone acrylamide (DAAM) at 70 °C to produce PATAC 100 −PDAAM x diblock copolymer spheres at 20% w/w solids via polymerization-induced self-assembly. Transmission electron microscopy and dynamic light scattering (DLS) analysis confirm that the mean sphere diameter can be adjusted by systematic variation of the mean degree of polymerization of the PDAAM block. Remarkably, DLS studies confirm that highly cationic PATAC 100 −PDAAM 1500 spheres retain their colloidal stability in the presence of either 4.0 M KCl or 3.0 M ammonium sulfate for at least 115 days at 20 °C. The mole fraction of PATAC chains within the stabilizer shell was systematically varied by the chain extension of various binary mixtures of nonionic poly(N,N-dimethylacrylamide) (PDMAC) and cationic PATAC with DAAM to produce ([n] PATAC 100 + [1 − n] PDMAC 67 )−PDAAM z diblock copolymer spheres at 20% w/w. DLS studies confirmed that a relatively high mole fraction of cationic PATAC stabilizer chains (n ≥ 0.75) is required for the dispersions to remain colloidally stable in 4.0 M KCl. Cationic worms and vesicles could also be synthesized using a binary mixture of PATAC and PDMAC precursors, where n = 0.10. However, the vesicles only remained colloidally stable up to 1.0 M KCl, whereas the worms proved to be stable up to 2.0 M KCl. Such block copolymer nanoparticles are expected to be useful model systems for understanding the behavior of aqueous colloidal dispersions in extremely salty media. Finally, zeta potentials determined using electrophoretic light scattering are presented for such nanoparticles dispersed in highly salty media.

A loading efficiency of up to 86% is achieved for silica nanoparticles encapsulated within crosslinkable redox-sensitive thermoresponsive diblock copolymer vesicles in water at 50 °C; triggered release is also demonstrated for this system.