A Simple and Facile Approach to Aliphatic N-Substituted Functional Eight-Membered Cyclic Carbonates and Their Organocatalytic Polymerization
Abstract
Aliphatic N-substituted functional eight-membered cyclic carbonates were synthesized from N-substituted diethanolamines by intramolecular cyclization. On the basis of the N-substituent, three major subclasses of carbonate monomers were synthesized (N-aryl, N-alkyl and N-carbamate). Organocatalytic ring opening polymerization (ROP) of eight-membered cyclic carbonates was explored as a route to access narrowly dispersed polymers of predictable molecular weights. Polymerization kinetics was highly dependent on the substituent on the nitrogen atom and the catalyst used for the reaction. The use of triazabicyclodecene (TBD), instead of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), as the catalyst for the N-alkyl substituted monomers significantly enhanced the rate of polymerizations. Computational studies were performed to rationalize the observed trends for TBD catalyzed polymerizations. With the optimal organocatalyst all monomers could be polymerized generating well-defined polymers within a timespan of ≤2 h with relatively high monomer conversion (≥80%) and low molar-mass dispersity (Đ(M) ≤ 1.3). Both the glass transition temperatures (T(g)) and onset of degradation temperatures (T(onset)) of these polymers were found to be N-substituent dependent and were in the range of about -45 to 35 °C and 230 to 333 °C, respectively. The copolymerization of the eight membered monomers with 6-membered cyclic comonomers including commercially available l-lactide and trimethylene carbonate produced novel copolymers. The combination of inexpensive starting materials, ease of ring-closure and subsequent polymerization makes this an attractive route to functional polycarbontes.
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N-substitution not only enhances the ring strain but also provides a synthetic handle to introduce functionality to these polycarbonates.
“The N-substitution not only enhances the ring strain but also provides a synthetic handle to introduce functionality to these polycarbonates.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [283]
A class of strained 8-membered cyclic carbonates derived from diethanolamine were prepared and polymerized to well-defined N-substituted polycarbonates.
“Recently a class of strained 8-memebered cyclic carbonates derived from diethanolamine were prepared and polymerized to well-defined N-substituted polycarbonates.283,284”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [283]
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- Authors
- Venkataraman, S., Ng, V. W. L., Coady, D. J., Horn, H. W., Jones, G. O., Fung, T. S., Sardon, H., Waymouth, R. M., Hedrick, J. L., & Yang, Y. Y.
- Affiliations
- Institute of Bioengineering and Nanotechnology (SG)
- IBM Research - Almaden (US)
- POLYMAT, University of the Basque Country UPV/EHU Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia-San Sebastián, Spain
- Stanford University (US)
- Corresponding author
- Hedrick, James L.
- Yang, Yi Yan
- ORCID
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-10-26
- Volume
- 137
- Issue
- 43
- Pages
- 13851-13860
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2410418118
- Semantic Scholar
- 378a9778a1919c95beb3aa03528faa97c1691ea8
- Cited by
- 97
- References
- 53
- Citations by year
- 2026: 3 · 2025: 8 · 2024: 4 · 2023: 8 · 2022: 12 · 2021: 7 · 2020: 7 · 2019: 10 · 2018: 20 · 2017: 11 · 2016: 7
- FWCI
- 4.77
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Division of Chemistry (CHE-1306730)
- International Business Machines Corporation
- Institute of Bioengineering and Nanotechnology
- Topics
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- intramolecular cyclization, organocatalytic ring-opening polymerization, polymerization kinetics, glass transition temperature, thermal stability, copolymerization, L-lactide, trimethylene carbonate, polycarbonate
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