In situ cross-linking polymerization-induced self-assembly not only generates cross-linked structures but also promotes morphology transition by the cross-linker

Abstract

Compared with the post-polymerization cross-linking strategy, in situ cross-linking by divinyl comonomers in polymerization-induced self-assembly (PISA) is a more straightforward and convenient approach to produce structurally stabilized nano-objects. However, cross-linking...

Greatly Enhanced Accessibility and Reproducibility of Worm‐like Micelles by In Situ Crosslinking Polymerization‐Induced Self‐Assembly

“…For example, spherical micelles of PEG 90 ‐ b ‐PBzMA x were formed at DP PBzMA =40, 50, 60 and 70, but the mixture of spherical micelles and worm‐like micelles or pure worm‐like micelles were formed at the same DP PBzMA of PEG 90 ‐ b ‐P(BzMA x ‐ co ‐HBMA 1 ); worm‐like micelles of PEG 90 ‐ b ‐PBzMA x were formed at DP PBzMA =80 and 90, but PEG 90 ‐ b ‐P(BzMA x ‐ co ‐HBMA 1 ) vesicles were formed at the same DP PBzMA . The promoted effect on morphological transition is mainly attributed to the branched structures of the solvophobic blocks, which is in accordance with the previous report [51] . Moreover, prevented effect on morphology transition in these in situ crosslinking PISA cases (HBMA/PEG 90 ‐CPADB=1/1) was not observed because crosslinked structures of the solvophobic P(BzMA x ‐ co ‐HBMA 1 ) blocks were not formed under these conditions (Figure S8).…”

“…In situ crosslinking PISA has been reported to fabricate crosslinked nano‐objects in one‐pot, [49–53] but the enhanced accessibility and reproducibility of worm‐like micelles by in situ crosslinking PISA has never been investigated. In the previous studies, [49–53] the feed molar ratio of the crosslinker/monomer was usually designed as a fixed value in a series of comparative experiments, resulting in similar crosslinking densities of the nano‐objects with different chain lengths of solvophobic blocks.…”

Organic–inorganic hybrid nanomaterials prepared via polymerization-induced self-assembly: recent developments and future opportunities

“…Over the past decade or so, the development of polymerization-induced self-assembly (PISA) has enabled the preparation of concentrated block copolymer nanomaterials (10–50% w/w solids) with a diverse set of morphologies including spheres, worms, vesicles, large-compound vesicles, nanotubes, etc . 31–82 During PISA, the formation and in situ self-assembly of block copolymers occur at the same time, making the mechanism of PISA much more complicated than the traditional self-assembly method. A variety of polymerization techniques has been introduced into PISA including reversible addition–fragmentation chain transfer (RAFT) polymerization, 31,35,83 atom transfer radical polymerization (ATRP), 84,85 nitroxide mediated polymerization (NMP), 86,87 ring-opening metathesis polymerization (ROMP), 88,89 ring-opening polymerization (ROP), 90,91 living anionic polymerization (LAP), 92 and organotellurium-mediated radical polymerization (TERP).…”

Influence of solvent on the RAFT-mediated polymerization of benzyl methacrylate (BzMA) and how to overcome the thermodynamic/kinetic limitation of morphology evolution during polymerization-induced self-assembly

“…19–38 Compared with traditional self-assembly, PISA effectively simplifies the preparation of nano-objects and can fabricate nanoparticles at very high concentrations (10–50 wt%), providing the possibility for the large-scale production of polymeric nanomaterials. In principle, all the controlled/living polymerization approaches can be used in PISA, such as reversible addition–fragmentation chain transfer (RAFT) polymerization, 39–46 atom transfer radical polymerization (ATRP), 47–49 nitroxide-mediated radical polymerization (NMP), 50–52 and ring-opening metathesis polymerization (ROMP). 53–58 Nevertheless, the majority of the reported PISA examples are based on RAFT polymerization, which might be due to the extensive tolerance of various functional monomers and solvents to this polymerization technique.…”

“…53–58 Nevertheless, the majority of the reported PISA examples are based on RAFT polymerization, which might be due to the extensive tolerance of various functional monomers and solvents to this polymerization technique. 19–46 Depending on the solubility of monomers in the polymerization medium, PISA is carried out via either dispersion polymerization (good solubility of the monomer) or emulsion polymerization (poor solubility of the monomer). Generally, in a PISA process, the chain length of the solvophilic blocks (stabilizers) is fixed, and the chain extension of the solvophobic blocks induces the morphology transition of the resultant nano-objects from spherical micelles, to worm-like micelles, and then to vesicles.…”