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Epoxy-based polymer networks from step-growth polymerizations are ubiquitous in coatings, adhesives, and as matrices in composite materials. Dynamic covalent bonds in the network allow its degradation into small molecules and thus, enable chemical recycling; however, such degradation often requires elevated temperatures and costly chemicals, resulting in various small molecules. Here, we design crosslinked polyesters from structurally similar epoxy and anhydride monomers derived from phthalic acid. We achieve selective degradation of the polyesters through transesterification reactions at near-ambient conditions using an alkali carbonate catalyst, resulting in a singular phthalic ester. We also demonstrate upcycling the network polyesters to photopolymers by one-step depolymerization using a functional alcohol.
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Stereocomplexation of Stereoregular Aliphatic Polyesters: Change from Amorphous to Semicrystalline Polymers with Single Stereocenter Inversion
Stereocomplexation is a useful strategy for the enhancement of polymer properties by the co-crystallization of polymer strands with opposed chirality. Yet, with the exception of PLA, stereocomplexes of biodegradable polyesters are relatively underexplored and the relationship between polymer microstructure and stereocomplexation remains to be delineated, especially for copolymers comprising two different chiral monomers. In this work, we resolved the two enantiomers of a non-symmetric chiral anhydride (CPCA) and prepared a series of polyesters from different combinations of racemic and enantiopure epoxides and anhydrides, via metal-catalyzed ring-opening copolymerization (ROCOP). Intriguingly, we found that only specific chiral combinations between the epoxide and anhydride building blocks result in the formation of semicrystalline polymers, with a single stereocenter inversion inducing a change from amorphous to semicrystalline copolymers. Stereocomplexes of the latter were prepared by mixing an equimolar amount of the two enantiomeric copolymers, yielding materials with increased melting temperatures (ca. 20 °C higher) compared to their enantiopure constituents. Following polymer structure optimization, the stereocomplex of one specific copolymer combination exhibits a particularly high melting temperature (Tm = 238 °C).
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- PAR ID:
- 10324154
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- ISSN:
- 0002-7863
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/jacs.2c02981
