Polylactones 12. Cationic polymerization of 2,2‐dimethyltrimethylene carbonate
Abstract
The polymerization of 2,2‐dimethyltrimethylene carbonate (1) was initiated with borontrifluoride etherate, trifluoromethanesulfonic acid (triflic acid), methyl triflate and ethyl fluorosulfate. The reaction was studied at 20, 50, 80 and 120°C in 1,2‐dichloroethane and nitrobenzene. Methyl triflate and triflic acid turned out to be the most reactive initiators. Yet, due to “black biting” degradation, yields > 80% were never obtained. With BF 3 etherate yields up to 98% and molecular weights (M̄n) up to 5200 g/mol were found. From 1 H NMR and IR spectra it can be deduced that methyl triflate alkylates the exocyclic oxygen (carbonyl group) and the resulting carbenium ion reacts with its counterion by ring‐opening of the alkyl‐oxygen bond. The oligomers and polymers formed in this way initially possess methyl (or ethyl) carbonate groups at one end and triflate groups at the other end of the chain. Elemental analyses and IR spectra prove that no carbon dioxide is lost in the course of the cationic polymerization. DSC measurements showed that crystallinity and melting points of poly(1) largely depend on the polymerization conditions in contrast to the glass transition temperature.
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The synthesis of high molecular weight polymers is rather difficult with cationic catalysts due to the strong tendency of intramolecular transesterification (cyclization) and proton transfer reactions of the cationic propagating species.
“The synthesis of high molecular weight polymers is rather difficult with these catalysts due to the strong tendency of intramolecular transesterification (cyclization) and proton transfer reactions of the cationic propagating species.288”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [288]
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- Authors
- Kricheldorf, H. R., Dunsing, R., & Albet, A. S. I.
- Affiliations
- Universität Hamburg (DE)
- Corresponding author
- Kricheldorf, Hans R.
- ORCID
- Kricheldorf, Hans R.
- Venue
- Die Makromolekulare Chemie
- Publisher
- Wiley
- Published
- 1987-10
- Volume
- 188
- Issue
- 10
- Pages
- 2453-2466
- ISSN
- 0025-116X (ISSN-L)
- OpenAlex
- W1523663740
- Cited by
- 93
- References
- 10
- Citations by year
- 2025: 1 · 2024: 2 · 2022: 1 · 2021: 2 · 2020: 1 · 2019: 4 · 2018: 1 · 2017: 4 · 2016: 3 · 2015: 1 · 2014: 1 · 2013: 2 · 2012: 1
- FWCI
- 1.55
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Die Makromolekulare Chemie (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- 2,2-dimethyltrimethylene carbonate, cationic polymerization, polylactones, boron trifluoride etherate, trifluoromethanesulfonic acid, methyl triflate, carbenium ions, ring-opening polymerization, crystallinity, melting point, glass transition temperature, molecular weight
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