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Synthesis of Polymers From Bio-Based Methacrylates Comprising Aromatic or Aliphatic Structures Using NIR-Mediated
Nicolai Meckbach1, Lea Viktoria Rubbert1, Bernd Strehmel1
1Institute for Coatings and Surface Chemistry, Faculty of Chemistry, Niederrhein University of Applied Sciences, Krefeld, Germany.
Macromolecular Rapid Communications
|November 9, 2025
Summary
Near-infrared-mediated atom transfer radical polymerization (ATRP) synthesized polymethacrylates from bio-based monomers. Bio-based polymers showed broader dispersity and varied solubility compared to poly(methyl methacrylate).
Area of Science:
- Polymer Chemistry
- Organic Synthesis
- Materials Science
Background:
- Developing sustainable polymers from bio-based resources is crucial for reducing reliance on petrochemicals.
- Atom Transfer Radical Polymerization (ATRP) offers controlled synthesis of polymers with defined architectures.
- Near-infrared (NIR) light can mediate ATRP, enabling polymerization under mild conditions.
Purpose of the Study:
- To synthesize polymethacrylates using NIR-mediated ATRP from novel bio-based monomers.
- To compare the properties of these bio-based polymers with poly(methyl methacrylate) (PMMA).
- To investigate the synthesis and properties of block copolymers incorporating bio-based monomers.
Main Methods:
- NIR-mediated ATRP was employed using a heptamethine cyanine sensitizer and a copper complex deactivator.
- Polymerization was conducted at 790 nm excitation wavelength.
- Synthesized homopolymers and block copolymers were characterized for yield, molecular weight, dispersity, glass transition temperature, and solubility.
Main Results:
- Bio-based polymethacrylates exhibited broader dispersity than PMMA, suggesting increased chain termination.
- All synthesized macroinitiators were chain extendable, forming block copolymers.
- Block copolymers from bio-based monomers showed distinct solubility differences due to their unique ester structures, with lower initiation efficiency observed for one isomer mixture compared to methyl methacrylate.
Conclusions:
- NIR-mediated ATRP is a viable method for synthesizing polymethacrylates from bio-based monomers.
- The bio-based polymers present unique properties, including broader dispersity and varied solubility, offering potential for specialized applications.
- Further research into initiation efficiency and structural influences is warranted for optimizing bio-based polymer synthesis.
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