Benzyl methacrylate (BzMA) is polymerized using a poly(lauryl methacrylate) macromolecular chain transfer agent (PLMA macro-CTA) using reversible addition–fragmentation chain transfer (RAFT) polymerization at 70 °C in n-dodecane. This choice of solvent leads to an efficient dispersion polymerization, with polymerization-induced self-assembly (PISA) occurring via the growing PBzMA block to produce a range of PLMA–PBzMA diblock copolymer nano-objects, including spheres, worms, and vesicles. In the present study, particular attention is paid to the worm phase, which forms soft free-standing gels at 20 °C due to multiple inter-worm contacts. Such worm gels exhibit thermo-responsive behavior: heating above 50 °C causes degelation due to the onset of a worm-to-sphere transition. Degelation occurs because isotropic spheres interact with each other much less efficiently than the highly anisotropic worms. This worm-to-sphere thermal transition is essentially irreversible on heating a dilute solution (0.10% w/w) but is more or less reversible on heating a more concentrated dispersion (20% w/w). The relatively low volatility of n-dodecane facilitates variable-temperature rheological studies, which are consistent with eventual reconstitution of the worm phase on cooling to 20 °C. Variable-temperature ¹H NMR studies conducted in d₂₆-dodecane confirm partial solvation of the PBzMA block at elevated temperature: surface plasticization of the worm cores is invoked to account for the observed change in morphology, because this is sufficient to increase the copolymer curvature and hence induce a worm-to-sphere transition. Small-angle X-ray scattering and TEM are used to investigate the structural changes that occur during the worm-to-sphere-to-worm thermal cycle; experiments conducted at 1.0 and 5.0% w/w demonstrate the concentration-dependent (ir)reversibility of these morphological transitions.

Well-defined poly(lauryl methacrylate-benzyl methacrylate) (PLMA-PBzMA) diblock copolymer nanoparticles are prepared in n-heptane at 90 °C via reversible addition–fragmentation chain transfer (RAFT) polymerization. Under these conditions, the PLMA macromolecular chain transfer agent (macro-CTA) is soluble in n-heptane, whereas the growing PBzMA block quickly becomes insoluble. Thus this dispersion polymerization formulation leads to polymerization-induced self-assembly (PISA). Using a relatively long PLMA macro-CTA with a mean degree of polymerization (DP) of 37 or higher leads to the formation of well-defined spherical nanoparticles of 41 to 139 nm diameter, depending on the DP targeted for the PBzMA block. In contrast, TEM studies confirm that using a relatively short PLMA macro-CTA (DP = 17) enables both worm-like and vesicular morphologies to be produced, in addition to the spherical phase. A detailed phase diagram has been elucidated for this more asymmetric diblock copolymer formulation, which ensures that each pure phase can be targeted reproducibly. ¹H NMR spectroscopy confirmed that high BzMA monomer conversions (>97%) were achieved within 5 h, while GPC studies indicated that reasonably good blocking efficiencies and relatively low diblock copolymer polydispersities (M_w/M_n < 1.30) were obtained in most cases. Compared to prior literature reports, this all-methacrylic PISA formulation is particularly novel because: (i) it is the first time that higher order morphologies (e.g. worms and vesicles) have been accessed in non-polar solvents and (ii) such diblock copolymer nano-objects are expected to have potential boundary lubrication applications for engine oils.

Industrially-sourced mineral oil and a poly(α-olefin) are used as solvents for the reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) using a poly(lauryl methacrylate) macromolecular chain transfer agent (PLMA macro-CTA) at 90 °C. The insolubility of the growing PBzMA chains under such conditions leads to polymerization-induced self-assembly (PISA), whereby poly(lauryl methacrylate)-poly(benzyl methacrylate) (PLMA-PBzMA) diblock copolymer spheres, worms or vesicles are produced directly as concentrated dispersions. The particular diblock copolymer composition required to access each individual morphology depends on the nature of the oil. Moreover, the solvent type also affects important properties of the physical free-standing gels that are formed by the PLMA-PBzMA worm dispersions, including the storage modulus (G′), critical gelation temperature (CGT) and critical gelation concentration (CGC). Spherical PLMA-PBzMA diblock copolymer nanoparticles can be prepared at up to 50% w/w solids and an efficient ‘one-pot’ protocol involving solution polymerization of LMA followed immediately by dispersion polymerization of BzMA has been developed. The latter formulation enables high BzMA conversions to be achieved, with spherical nanoparticles being produced at 30% w/w solids.

Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) is utilized to prepare a series of poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nano-objects at 90 °C directly in mineral oil. Polymerization-induced self-assembly (PISA) occurs under these conditions, with the resulting nanoparticles exhibiting spherical, worm-like or vesicular morphologies when using a relatively short PSMA₁₃ macromolecular chain transfer agent (macro-CTA), as confirmed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. Only kinetically-trapped spherical nanoparticles are obtained when using longer macro-CTAs (e.g. PSMA₁₈ or PSMA₃₁), with higher mean degrees of polymerization (DPs) for the PBzMA core-forming block simply producing progressively larger spheres. SAXS is used for the first time to monitor the various morphological transitions that occur in situ during the RAFT dispersion polymerization of BzMA when targeting either spheres or vesicles as the final copolymer morphology. This powerful characterization technique enables the evolution of particle diameter, mean aggregation number, number of copolymer chains per unit surface area (S_agg) and the distance between adjacent copolymer chains at the core–shell interface (d_int) to be monitored as a function of monomer conversion for kinetically-trapped spheres. Moreover, the gradual evolution of copolymer morphology during PISA is confirmed unequivocally, with approximate ‘lifetimes’ assigned to the intermediate pure sphere and worm morphologies when targeting PSMA₁₃–PBzMA₁₅₀ vesicles. Within vesicle phase space, the membrane thickness (T_m) increases monotonically with PBzMA DP. Furthermore, a combination of dynamic light scattering (DLS), TEM and post mortem SAXS studies indicate that the lumen volume is reduced while the overall vesicle dimensions remain essentially constant. Thus the constrained vesicles grow inwards, as recently reported for an aqueous PISA formulation. This suggests a universal vesicle growth mechanism for all PISA formulations.