Accurate structural control and block formation in the living polymerization of 1, 3-dienes by nitroxide-mediated procedures
Abstract
The living free radical polymerization of 1,3-dienes, such as isoprene and 1,3-butadiene, has been shown to be a facile process in the presence of alkoxyamine initiators based on a 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxy, 2, skeleton. These α-hydrido nitroxide derivatives were able to control the homopolymerization to high conversion and molecular weights from 1000 to 100 000 amu with polydispersities of 1.06−1.15 readily obtained. Block and random copolymers based on combinations of 1,3-dienes with a variety of functionalized vinyl monomers, such as styrene, acrylate, or methacrylate derivatives, could also be prepared with similar control. In comparison with 2,2,6,6-tetramethylpiperidinoxy (TEMPO), these new systems represent a dramatic improvement in the ability to control the polymerization of 1,3-dienes and further demonstrate the versatility of nitroxide-mediated living free radical procedures.
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In comparison with conventional TEMPO systems, these new NMP systems exhibit significant improvement in the ability to control polymerization and demonstrate the versatility of nitroxide-mediated living free radical procedures.
“In comparison with conventional TEMPO systems, these new systems exhibit a significant improvement in the ability to control the polymerization and further demonstrate the versatility of nitroxide-mediated living free radical procedures [37].”
From Block Copolymers: Synthesis, Self-Assembly, and Applications (2017) · cites this paper as [37]
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“In comparison with conventional TEMPO systems, these new systems exhibit a significant improvement in the ability to control the polymerization and further demonstrate the versatility of nitroxide-mediated living free radical procedures [37].”
Background
- Authors
- Benoit, D., Harth, E., Fox, P., Waymouth, R. M., & Hawker, C. J.
- Affiliations
- IBM Research - Almaden (US)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2000-01-01
- Volume
- 33
- Issue
- 2
- Pages
- 363-370
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1991534816
- Cited by
- 216
- References
- 57
- Citations by year
- 2026: 3 · 2025: 1 · 2024: 2 · 2023: 1 · 2022: 3 · 2021: 7 · 2020: 7 · 2019: 11 · 2018: 16 · 2017: 6 · 2016: 9 · 2015: 4 · 2014: 5 · 2013: 7 · 2012: 16
- FWCI
- 11.32
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Keywords
- nitroxide-mediated polymerization, controlled radical polymerization, conjugated dienes, isoprene, 1,3-butadiene, alkoxyamine initiators, block copolymers, random copolymers, styrene, acrylates, methacrylates, molecular weight control, polydispersity
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