Recent developments in entropy-driven ring-opening metathesis polymerization: mechanistic considerations, unique functionality, and sequence control

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@article{9b7b0a8e62e34364b8f03735a746ac84,
title = "Recent developments in entropy-driven ring-opening metathesis polymerization: mechanistic considerations, unique functionality, and sequence control",
abstract = "Entropy‐driven ROMP (ED‐ROMP) involves polymerization of olefin‐containing macrocyclic monomers under entropically favorable conditions. Macrocycles can be prepared from a variety of interesting molecules which, when polymerized, impart unique functionality to the resulting polymer backbone such as degradable linkages, biological moieties, crystallizable groups, or supramolecular hosts. In addition, the sequence of atoms in the cyclic monomer is preserved within the polymer repeating units, allowing for facile preparation of sequence‐defined polymers. In this review article, we consider how the mechanism of ROMP applies to ED polymerizations, how olefinic macrocycles are synthesized, and how polymerization conditions can be tuned to maximize conversion. Recent works in the past 10 years are highlighted, with emphasis on methods which can be employed to achieve fast polymerization kinetics and/or selective head‐to‐tail regiochemistry, thus improving polymerization control. ED‐ROMP, with its unique capability to produce polymers with well‐defined polymer backbone microstructure, represents an essential complement to other, well‐established, metathesis methodologies such as ROMP.",
keywords = "controlled polymerization, cyclic olefins, degradable polymers, host-guest chemistry, semicrystalline polymers",
author = "A.K. Pearce and J.C. Foster and R.K. O'Reilly",
year = "2019",
month = aug,
day = "1",
doi = "10.1002/pola.29428",
language = "English",
volume = "57",
pages = "1621--1634",
journal = "Journal of Polymer Science. Part A: Polymer Chemistry",
issn = "0887-624X",
publisher = "Wiley",
number = "15",

}

RIS

TY - JOUR

T1 - Recent developments in entropy-driven ring-opening metathesis polymerization

T2 - mechanistic considerations, unique functionality, and sequence control

AU - Pearce, A.K.

AU - Foster, J.C.

AU - O'Reilly, R.K.

PY - 2019/8/1

Y1 - 2019/8/1

N2 - Entropy‐driven ROMP (ED‐ROMP) involves polymerization of olefin‐containing macrocyclic monomers under entropically favorable conditions. Macrocycles can be prepared from a variety of interesting molecules which, when polymerized, impart unique functionality to the resulting polymer backbone such as degradable linkages, biological moieties, crystallizable groups, or supramolecular hosts. In addition, the sequence of atoms in the cyclic monomer is preserved within the polymer repeating units, allowing for facile preparation of sequence‐defined polymers. In this review article, we consider how the mechanism of ROMP applies to ED polymerizations, how olefinic macrocycles are synthesized, and how polymerization conditions can be tuned to maximize conversion. Recent works in the past 10 years are highlighted, with emphasis on methods which can be employed to achieve fast polymerization kinetics and/or selective head‐to‐tail regiochemistry, thus improving polymerization control. ED‐ROMP, with its unique capability to produce polymers with well‐defined polymer backbone microstructure, represents an essential complement to other, well‐established, metathesis methodologies such as ROMP.

AB - Entropy‐driven ROMP (ED‐ROMP) involves polymerization of olefin‐containing macrocyclic monomers under entropically favorable conditions. Macrocycles can be prepared from a variety of interesting molecules which, when polymerized, impart unique functionality to the resulting polymer backbone such as degradable linkages, biological moieties, crystallizable groups, or supramolecular hosts. In addition, the sequence of atoms in the cyclic monomer is preserved within the polymer repeating units, allowing for facile preparation of sequence‐defined polymers. In this review article, we consider how the mechanism of ROMP applies to ED polymerizations, how olefinic macrocycles are synthesized, and how polymerization conditions can be tuned to maximize conversion. Recent works in the past 10 years are highlighted, with emphasis on methods which can be employed to achieve fast polymerization kinetics and/or selective head‐to‐tail regiochemistry, thus improving polymerization control. ED‐ROMP, with its unique capability to produce polymers with well‐defined polymer backbone microstructure, represents an essential complement to other, well‐established, metathesis methodologies such as ROMP.

KW - controlled polymerization

KW - cyclic olefins

KW - degradable polymers

KW - host-guest chemistry

KW - semicrystalline polymers

UR - http://www.scopus.com/inward/record.url?scp=85068227408&partnerID=8YFLogxK

U2 - 10.1002/pola.29428

DO - 10.1002/pola.29428

M3 - Review article

VL - 57

SP - 1621

EP - 1634

JO - Journal of Polymer Science. Part A: Polymer Chemistry

JF - Journal of Polymer Science. Part A: Polymer Chemistry

SN - 0887-624X

IS - 15

ER -