Polymerization Induced Microphase Separation for the Fabrication of Nanostructured Materials

Abstract

Polymerization induced microphase separation (PIMS) is a strategy used to develop unique nanostructures with highly useful morphologies through the microphase separation of emergent block copolymers during polymerization. In this process, nanostructures are formed with at least two chemically independent domains, where at least one domain is composed of a robust crosslinked polymer. Crucially, this synthetically simple method is readily used to develop nanostructured materials with the highly coveted co‐continuous morphology, which can also be converted into mesoporous materials by selective etching of one domain. As PIMS exploits a block copolymer microphase separation mechanism, the size of each domain can be tightly controlled by modifying the size of block copolymer precursors, thus providing unparalleled control over nanostructure and resultant mesopore sizes. Since its inception 11 years ago, PIMS has been used to develop a vast inventory of advanced materials for an extensive range of applications including biomedical devices, ion exchange membranes, lithium‐ion batteries, catalysis, 3D printing, and fluorescence‐based sensors, among many others. In this review, we provide a comprehensive overview of the PIMS process, summarize latest developments in PIMS chemistry, and discuss its utility in a wide variety of relevant applications.

From Unregulated Networks to Designed Microstructures: Introducing Heterogeneity at Different Length Scales in Photopolymers for Additive Manufacturing

“…Such macroCTAs are initially soluble in acrylic resins but become insoluble as RAFT photopolymerization progresses. 302 The oligomeric nature of the CTA stimulates phase separation at an early stage of the polymerization process. Furthermore, efficient RAFT kinetics delayed the gel point effectively, allowing the components to diffuse until later stages of the polymerization process and hence enhancing phase separation.…”

“…Only the realization of the underlying fundamental effects causing PhIPS has allowed the development of this concept. 302 Finally, we suggest utilizing the tremendous number of findings available for heterogeneous thermoplastic polymers in general and translating successful strategies to the realm of photopolymers. Successful translation, however, is only possible if we approach this task interdisciplinarily with chemists supplying new monomers and polymerization strategies to enlarge the range of accessible microstructures, material scientists and physicists analyzing the impact of various microstructures on material behavior, and engineers supplying new AMTs.…”

“…In addition to monomer composition and irradiation intensity, other kinetics-related parameters including the type and content of photoinitiator and the sequence of cross-linking (for orthogonal thermal/photocuring systems) govern the PhIPS mechanism and morphology. For further insights on process–microstructure correlations, there are several reviews available, which specifically focus on this aspect. , …”

In Situ Visualization of Polymerization-Induced Phase Separation for 3D-Printing of Porous Architectures

“…Recently, Dong et al , described adaptations to these materials that are tailored toward 3D printing in a digital light processing (DLP)-based printing process. By completely omitting porogenic solvents, polymerization-induced microphase separation makes use of the self-assembly of block copolymers to yield porous structures for various applications. , …”

Controlled Asymmetric Lamellar Nanomorphology Obtained through Nitroxide-Mediated Polymerization-Induced Microphase Separation

“…In the present work, we explore how polymerization-induced microphase separation (PIMS) process can be advantageous to produce straightforward A-LAM morphologies. Among the reaction-induced phase-transitions (RIPTs), PIMS is an original, versatile, and solvent-free method to prepare out-of-equilibrium bulk nanostructured polymer materials in a single step. , PIMS process involves polymerization of monomers in the presence of a reactive homopolymer in order to produce in situ BCP with two incompatible blocks self-assembling simultaneously to polymerization. One of the pioneer work in this field was dedicated to the synthesis of high-impact polystyrene from reactive polybutadiene dissolved in styrene monomer .…”