Cited by 93biodegradable polymer synthesis and propertiesAdvanced Polymer Synthesis and CharacterizationCarbon dioxide utilization in catalysis

Polylactones 12. Cationic polymerization of 2,2‐dimethyltrimethylene carbonate

Kricheldorf, Hans R., Dunsing, Ruth, Albet, Angels Serra i·1987·Die Makromolekulare Chemie

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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Crossref · 10.1002/macp.1987.021881020

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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.
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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