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Ring-opening metathesis polymerization (ROMP) has been widely used for the synthesis of functional polymers. However, most ROMP-derived polymers are nondepolymerizable, limiting their sustainability and eco-friendiness. While recent advances in designing low-strain cyclic olefin monomers have enabled the ROMP synthesis of depolymerizable polyolefins, the scope of these monomers remains limited due to the narrow range of ring strain energies (RSEs = 4.7–5.4 kcal/mol) required to allow both polymerization and depolymerization in a closed-loop recycling process. Herein, we present a new class of chemically recyclable polyolefins based on cycloheptene derivatives with RSEs ranging from 3.8 to 7.2 kcal/mol. The wide range of RSEs enabled the establishment of a structure–polymerizability–depolymerizability relationship, shedding light on the role of RSE in both polymerization and depolymerization. A functional group transformation (FGT) strategy, harnessing reversible ketone-to-acetal chemistry, was developed to overcome the low polymerizability of low-strain monomers and the moderate depolymerizability of polymers made from moderate-strain monomers. This FGT approach not only enhanced the chemical recycling of moderately depolymerizable polyolefins but also provided access to highly depolymerizable polyolefins that are challenging to synthesize through direct ROMP of ultralow strain monomers. Moreover, the thermal properties of the chemically recyclable polyolefins developed in this study are highly tunable, with a broad range of glass transition temperatures (−7 to 104 °C), highlighting their potential for various applications.
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Synthesis of telechelic polyolefins
Telechelic polymers, polymers with two reactive end-groups, are sought after for their role in synthesizing macromolecules with complex structures such as multiblock copolymers and graft polymers. Many strategies for the synthesis of telechelic polymers from vinyl monomers using controlled radical polymerizations and anionic polymerizations exist. However, polyolefins—which account for the major fraction of polymer production—are not easily synthesized with two reactive end-groups. This difficulty is related to the sensitivity of olefin polymerization catalysts and their propensity for intramolecular chain transfer reactions. As a result, the most common strategies to access telechelic polyethylene and polypropylene (the two major polyolefins) do not rely on the insertion polymerization of ethylene nor propylene but rather on the polymerization of dienes or cyclic olefins. Nonetheless, recent advances in insertion polymerization and post-polymerization functionalization have resulted in the emergence of novel synthetic methods to access telechelic polyolefins. We here present a comprehensive review of all of these strategies to synthesize telechelic polyolefins.
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- Award ID(s):
- 1706911
- PAR ID:
- 10310811
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 12
- Issue:
- 36
- ISSN:
- 1759-9954
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1039/d1py00819f
