The importance of stereochemistry to the function of molecules is generally well understood. However, to date, control over stereochemistry and its potential to influence properties of the resulting polymers are, as yet, not fully realized. This Review focuses on the state of the art with respect to how stereochemistry in polymers has been used to influence and control their physical and mechanical properties, as well as begin to control their function. A brief overview of the synthetic methodology by which to access these materials is included, with the main focus directed towards the effect of stereochemistry on mechanical properties, biodegradation and conductivity. In addition, advances in applications of stereodefined polymers for enantioseparation and as supports for catalysts in asymmetric transformations are discussed. Finally, we consider the opportunities that the rich stereochemistry of sustainably sourced monomers might offer in this field. Where possible, we have drawn parallels between design principles in order to identify opportunities and limitations that these approaches may present in their effects on materials properties, performance and function.
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A.P.D. gratefully acknowledges financial support from the European Research Council (ERC, grant no 681559). J.C.W. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no 751150. S.J. and P.B. thank the European Commission for the financial support through SUSPOL-EJD 64267, while H.P. thanks The Leverhulme Trust (grant no RPG-2015-120) for financial support. M.L.B. acknowledges support from the National Science Foundation (DMR BMAT 1507420) and the W. Gerald Austen Endowed Chair from the John S. and James L. Knight Foundation.
The authors declare no competing interests.
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- Entanglement molecular weight
(Me). The molecular weight above which the material displays the characteristic properties of a plastic.
- Ring-opening polymerization
(ROP). A type of chain growth polymerization in which the end of the growing polymer chain reacts with a cyclic monomer, resulting in ring opening.
- Step-growth polycondensation
Multifunctional monomers combine to form dimers, trimers and oligomers before these ultimately combine to produce polymers.
- Chain-growth polymerization
Polymer chains are formed and grow by the addition of monomers one at a time to the end of a chain.
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Worch, J.C., Prydderch, H., Jimaja, S. et al. Stereochemical enhancement of polymer properties. Nat Rev Chem 3, 514–535 (2019). https://doi.org/10.1038/s41570-019-0117-z
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