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Cationic polymerization is a powerful strategy for the production of well-defined polymers and advanced materials. In particular, the emergence of living cationic polymerization has enabled pathways to complex polymer architectures inaccessible before. The use of light and electricity as external stimuli to regulate cationic polymerization represents another advance with increasing applications in surface fabrication and patterning, additive manufacturing, and other advanced material engineering. The past decade also witnessed vigorous progress in stereoselective cationic polymerizations, allowing for the dual control of both the tacticity and the molecular weight of vinyl polymers towards precision polymers. In addition, in addressing the plastics pollution crisis and achieving a circular materials economy, cationic polymerization offers unique advantages for generating chemically recyclable polymers, such as polyacetals, polysaccharides, polyvinyl ethers, and polyethers. In this review, we provide an overview of recent developments in regulating cationic polymerization, including emerging control systems, spatiotemporally controlled polymerization (light and electricity), stereoselective polymerization, and chemically recyclable/degradable polymers. Hopefully, these discussions will help to stimulate new ideas for the further development of cationic polymerization for researchers in the field of polymer science and beyond.
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Controlling Polymer Material Structure during Reaction-Induced Phase Transitions
Living systems are composed of a select number of biopolymers and minerals yet exhibit an immense diversity in materials properties. The wide-ranging characteristics, such as enhanced mechanical properties of skin and bone, or responsive optical properties derived from structural coloration, are a result of the multiscale, hierarchical structure of the materials. The fields of materials and polymer chemistry have leveraged equilibrium concepts in an effort to mimic the structure complex materials seen in nature. However, realizing the remarkable properties in natural systems requires moving beyond an equilibrium perspective. An alternative method to create materials with multiscale structures is to approach the issue from a kinetic perspective and utilize chemical processes to drive phase transitions. This Account features an active area of research in our group, reaction-induced phase transitions (RIPT), which uses chemical reactions such as polymerizations to induce structural changes in soft material systems. Depending on the type of phase transition (e.g., microphase versus macrophase separation), the resulting change in state will occur at different length scales (e.g., nm – μm), thus dictating the structure of the material. For example, the in situ formation of either a block copolymer or a homopolymer initially in a monomer mixture during a polymerization will drive nanoscale or macroscale transitions, respectively. Specifically, three different examples utilizing reaction-driven phase changes will be discussed: 1) in situ polymer grafting from block copolymers, 2) multiscale polymer nanocomposites, and 3) Lewis adduct-driven phase transitions. All three areas highlight how chemical changes via polymerizations or specific chemical binding result in phase transitions that lead to nanostructural and multiscale changes. Harnessing kinetic chemical processes to promote and control material structure, as opposed to organizing pre-synthesized molecules, polymers, or nanoparticles within a thermodynamic framework, is a growing area of interest. Trapping nonequilibrium states in polymer materials has been primarily focused from a polymer chain conformation viewpoint in which synthesized polymers are subjected to different thermal and processing conditions. The impact of reaction kinetics and polymerization rate on final polymer material structure is starting to be recognized as a new way to access different morphologies not available through thermodynamic means. Furthermore, kinetic control of polymer material structure is not specific to polymerizations and encompasses any chemical reaction that induce morphology transitions. Kinetically driven processes to dictate material structure directly impact a broad range of areas including separation membranes, biomolecular condensates, cell mobility, and the self-assembly of polymers and colloids. Advancing polymer material syntheses using kinetic principles such as RIPT opens new possibilities for dictating material structure and properties beyond what is currently available with traditional self-assembly techniques.
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- PAR ID:
- 10488642
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Accounts of Materials Research
- Volume:
- 4
- Issue:
- 9
- ISSN:
- 2643-6728
- Page Range / eLocation ID:
- 798 to 808
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/accountsmr.3c00071
