Self‐assembly behavior of amphiphilic linear‐block‐dendritic copolymers with long subchains: Dependences on dendron generation and mixing dynamics

Abstract

Block copolymers composed of acrylic acid and methyl methacrylate with three topologies of double linear blocks, poly(acrylic acid) (PAA) linear block/poly(methyl methacrylate) (PMMA) G1‐dendron and PAA linear block/PMMA G2‐dendron have been prepared by the combination of atom transfer radical polymerization and azide–alkyne click reaction. Proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and gel permeation chromatography have been adopted thoroughly to identify the chemical structure of those block copolymers with expected topologies. The self‐assembly of those block copolymers in the selective solvent has been performed through two mixing routes of gentle and abrupt variation in solvent selectivity, and the morphology of the obtained self‐assemblies/aggregates was observed by transmission electron microscopy. Because the abrupt variation route altered sharply the solvent quality during the mixing, the intermolecular association of polymer chains resulted in the smaller self‐assemblies but the further growth of smaller self‐assemblies was not observed. On the contrary, the gentle variation route changed gradually the solvent quality during the mixing, favoring not only the intermolecular association but also the further growth of self‐assemblies to result in larger aggregates. The final morphology of those assemblies/aggregates also exhibited the dependence of PMMA dendron generation. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1446–1456

Click chemistry strategies for the accelerated synthesis of functional macromolecules

“…526 The resulting dendritic macromolecules or dendrimers could also be used to construct more complex BCPs (dendritic-linear structure). 527,528 An ABA-type triblock dendronpolymer conjugate was constructed from dendrons with anthracene groups at the focal point and linear PEG building blocks end-capped with masked maleimides. Similarly, using furan instead of anthracene, thermally reversible dendronized step-polymers were constructed.…”

“…Synthetically, complex dendritic/dendrimer‐like architectures are achieved through the combination of CuAAC and ATRP in one‐pot with a shared Cu(I) catalyst 526 . The resulting dendritic macromolecules or dendrimers could also be used to construct more complex BCPs (dendritic‐linear structure) 527,528 . An ABA‐type triblock dendron–polymer conjugate was constructed from dendrons with anthracene groups at the focal point and linear PEG building blocks end‐capped with masked maleimides.…”

Mimicking the Natural World with Nanoarchitectonics for Self‐Assembled Superstructures

“…SAXS, cryogenic TEM and AFM were employed to investigate the structure of synthesized PEÀ S, revealing wormlike core-shell nanoparticles. [41] Li [42] et al reported caterpillar-like micelles via selfassembly of amphiphilic linear-block-dendritic copolymers, synthesizing three block copolymers containing acrylic acid and methyl methacrylate. These polymers contained three topologies such as double linear blocks, poly(acrylic acid) (PAA) linear block/poly(methyl methacrylate) (PMMA) G1dendron and PAA linear block/PMMA G2-dendron, which were characterized by NMR, FTIR and gel permeation chromatography techniques.…”

“…Li [42] et al . reported caterpillar‐like micelles via self‐assembly of amphiphilic linear‐block‐dendritic copolymers, synthesizing three block copolymers containing acrylic acid and methyl methacrylate.…”