Synthesis of High χ–Low N Diblock Copolymers by Polymerization‐Induced Self‐Assembly

Abstract

Polymerization‐induced self‐assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so‐called “high χ–low N” diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub‐10 nm surface features. By varying the degree of polymerization of the stabilizer and core‐forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre‐organization of copolymer chains within sterically‐stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution‐cast molecularly‐dissolved copolymer chains.

Fluorine-containing nano-objects with the same compositions but different segment distributions: synthesis, characterization and comparison

“…30 In view of the unique solubility of fluoropolymers in most common solvents, fluoropolymers have been introduced into the PISA system by researchers. [31][32][33][34][35][36][37][38][39][40][41][42] In contrast to other polymer systems, the fluorine-containing PISA system shows unique polymerization and self-assembly behaviour, and thus, distinct morphological evolution has been derived. 29,[31][32][33][34][35]43 UP to now, only a few fluorine-containing PISA protocols have been realized by employing fluorinated acrylates or fluorinated styrene as monomers.…”

Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly

“…After isolating PhBD 80 –PBzMA 40 from n ‐dodecane by precipitation into excess ethanol, the resulting dry copolymer powder was analyzed by SAXS over a wide temperature range (Figure S4). Only broad, low intensity peaks were observed at 40 °C, which suggests weak segregation within a relatively disordered non‐equilibrium phase that is formed following precipitation [67, 68] . However, thermal annealing drives further microphase separation, which leads to the appearance of several sharp peaks at higher q .…”

“…Only broad, low intensity peaks were observed at 40 8 8C, which suggests weak segregation within ar elatively disordered non-equilibrium phase that is formed following precipitation. [67,68] However, thermal annealing drives further microphase separation, which leads to the appearance of several sharp peaks at higher q. On heating above 100 8 8C, at least three equally spaced peaks are observed at q/q* = 1, 2and 3, indicating the formation of alamellar phase.…”

Solution self-assembly of fluorinated polymers, an overview

“…The transparency was due to the matching refractive indexes of PTriFEMA and n-alkane. 103,104 Such particles find use in smart (such as anti-reflective) coatings. Similarly to the work reported by Armes and co-workers, 101 Li's group reported a PISA process using a PMAA macro-CTA and PTriFEMA as the core-forming fluorinated polymer.…”