The construction of complex polymer architectures with well-defined topology, composition and functionality has been extensively explored as the molecular basis for the development of modern polymer materials. The unique reaction kinetics of free-radical polymerization leads to the concurrent formation of crosslinks between polymer chains and rings within an individual chain and, thus, free-radical (co)polymerization of multivinyl monomers provides a facile method to manipulate chain topology and functionality. Regulating the relative contribution of these intermolecular and intramolecular chain-propagation reactions is the key to the construction of architecturally complex polymers. This can be achieved through the design of new monomers or by spatially or kinetically controlling crosslinking reactions. These mechanisms enable the synthesis of various polymer architectures, including linear, cyclized, branched and star polymer chains, as well as crosslinked networks. In this Review, we highlight some of the contemporary experimental strategies to prepare complex polymer architectures using radical polymerization of multivinyl monomers. We also examine the recent development of characterization techniques for sub-chain connections in such complex macromolecules. Finally, we discuss how these crosslinking reactions have been engineered to generate advanced polymer materials for use in a variety of biomedical applications.
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The authors acknowledge the Science Foundation Ireland (SFI) Principal Investigator (PI) Programme (13/IA/1962) (to W.W.), National Science Foundation (NSF) Division of Materials Research (DMR) (1501324) (to K.M.), National Natural Science Foundation of China (NSFC) (51873179) (to W.W.), Senior Visiting Scholarship of State Key Laboratory of Molecular Engineering of Polymers, Fudan University (19FGJ07) (to W.W.), Irish Research Council (IRC) Employment-Based Postgraduate Programme (EBPPG/2018/159) (to J.L.) and University College Dublin (to Y.G.) for financial support. The authors apologize to those whose work is relevant but could not be cited owing to space limitations.
The authors declare no competing interests.
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- Intramolecular cyclization
In the context of free-radical polymerization, a special type of crosslinking reaction that produces a link similar to a standard crosslink but between two monomer units in the same primary chain, resulting in a loop structure.
- Instantaneous kinetic chain length
- Degree of branching
In radical polymerization of MVMs, degree of branching is defined as the number of branch points (that is, fully reacted MVMs) per repeat unit.
- ‘Grafting-from’ polymerization
A type of polymerization process in which initiating moieties are covalently bonded to the main polymer backbone and monomers are polymerized as side chains.
- ‘5-Å rule’
Effective intramolecular cyclization occurs only when two vinyl units are within 5 Å of one another.
- Mark–Houwink exponent (α)
A constant from the Mark–Houwink equation, which correlates the intrinsic viscosity ([𝜂]) of polymer with its molecular weight (M): [𝜂] = kMα. The α values depend on the configuration of polymer chains in the solvent environment.
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Gao, Y., Zhou, D., Lyu, J. et al. Complex polymer architectures through free-radical polymerization of multivinyl monomers. Nat Rev Chem 4, 194–212 (2020). https://doi.org/10.1038/s41570-020-0170-7
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