Renewable Polymers from Itaconic Acid by Polycondensation and Ring-Opening-Metathesis Polymerization
Abstract
Itaconic acid, a renewable feedstock obtained by fermentation of carbohydrates, is used as a key substrate to produce aliphatic unsaturated polyesters as well as polynorbornenes. Renewable unsaturated polyesters were prepared by direct polycondensation of dimethyl itaconate (DMI) with diols, whereas the ring-opening-metathesis polymerization (ROMP) of a DMI derived norbornene led to polynorbornenes. The direct polycondensation of DMI was performed with tin(II) ethylhexanoate as catalyst, 4-methoxyphenol as radical inhibitor, and different diols to yield linear unsaturated polyesters with a molecular weight up to 11 500 Da without isomerization or cross-linking of the vinylic double bond. Further modification of the unsaturated polyesters by thia-Michael addition yielded polysulfides, which were subsequently oxidized to polysulfones. Moreover, the solvent-free and straightforward Diels–Alder reaction of DMI and cyclopentadiene was used to prepare a partially renewable norbornene monomer, which was used in ROMP with different catalysts to prepare polymers with low dispersities and adjustable molecular weights. The thereof derived unsaturated and functionalized renewable polynorbornenes were further modified by hydrogenation, and their thermal properties were evaluated.
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This was the first time that a high-molecular-weight linear polyester was produced from itaconic acid without isomerization or cross-linking of the vinylic double bond.
“This was the first time that a high-molecular-weight linear polyester was produced from itaconic acid without isomerization or cross-linking of the vinylic double bond.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [233]
Further modification of the resulting unsaturated polyesters by Michael addition yielded polyesters with different substituents dangling off the backbone, which provided a means to tune the thermal property of the materials.
“Further modification of the resulting unsaturated polyesters by Michael addition yielded polyesters with different substituents dangling of the backbone, which provided a means to tune the thermal property of the materials.233”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [233]
Meier used Sn(Oct)2 to polymerize dimethyl itaconate and long chain diols in the presence of 0.5 wt% 4-methoxyphenol as a radical inhibitor to make linear unsaturated polyesters with Mn up to 11500 Da.
“Meier recently used Sn(Oct)2 to polymerize dimethyl itaconate and long chain diols in the presence of 0.5 wt% of 4-methoxyphenol as a radical inhibitor to make linear unsaturated polyesters with Mn up to 11500 Da. 233”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [233]
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- Authors
- Winkler, M., Lacerda, T. M., Mack, F., & Meier, M. A. R.
- Affiliations
- Karlsruhe Institute of Technology (DE)
- Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
- ORCID
- Lacerda, Talita M.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-02-20
- Volume
- 48
- Issue
- 5
- Pages
- 1398-1403
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2032463584
- Cited by
- 121
- References
- 36
- Citations by year
- 2026: 5 · 2025: 11 · 2024: 9 · 2023: 6 · 2022: 10 · 2021: 5 · 2020: 10 · 2019: 15 · 2018: 15 · 2017: 11 · 2016: 16 · 2015: 8
- FWCI
- 6.04
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Funders
- São Paulo Research Foundation (2013/02663-7)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Synthetic Organic Chemistry Methods
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- itaconic acid, bio-based polymers, dimethyl itaconate, polycondensation, ring-opening metathesis polymerization, norbornene polymers, unsaturated polyester resin, thia-Michael addition, polysulfides, polysulfone, Diels-Alder reaction, cyclopentadiene, 4-methoxyphenol, hydrogenation, thermal properties, molecular weight control
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