Methacrylate and Styrene Block Copolymer Synthesis by Cu-Mediated Chain Extension of Acrylate Macroinitiator in a Semibatch Reactor
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Authors
Cooze, Morgan J.
Deacon, Hayden M.
Phe, Katrina
Hutchinson, Robin Arthur
Date
2021-12-10
Type
journal article
Language
en
Keyword
Block copolymers , Cu-mediated polymerization , Methacrylates , Process development , Semibatch reactor , Styrene
Alternative Title
Abstract
A process for the well-controlled growth of acrylates by Cu-mediated polymerization has been developed, with macroinitiator synthesized continuously in a copper tubular reactor and subsequently chain-extended in a semibatch reactor without additional copper. Extending this process to methacrylates and styrene, however, has proven difficult due to a significant reduction in reaction rate. This barrier has been overcome by chain-extending the low molecular weight (Mn of 760 g mol–1) poly(methyl acrylate) macroinitiator with methacrylates and styrene using PMDETA (N,N,N′,N″,N″-pentamethyldiethylenetriamine) as ligand. Methyl methacrylate conversions of >80% at 70 °C and diethylene glycol methyl ether methacrylate conversions of >90% at room temperature are achieved in 4 h, with the same room temperature conditions successfully applied for controlled chain extensions with butyl methacrylate. Although styrene conversions are slightly lower (60–70%) over 4 h at 85 °C, the rates achieved are substantially higher than achieved in other studies. Hydrophobic–hydrophilic triblock structures are produced through sequential monomer feeds to the semibatch reactor, keeping total reaction time to less than 5 h. The ability to incorporate methacrylates and/or styrene into structured block polymers greatly extends the range of products that can be efficiently synthesized with low copper levels by this process.
Description
This is the peer reviewed version of the following article: Cooze, M.J., Deacon, H.M., Phe, K. and Hutchinson, R.A. (2022), Methacrylate and Styrene Block Copolymer Synthesis by Cu-Mediated Chain Extension of Acrylate Macroinitiator in a Semibatch Reactor. Macromol. React. Eng. 2100043., which has been published in final form at https://doi.org/10.1002/mren.202100043. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Citation
Cooze, M.J., Deacon, H.M., Phe, K. and Hutchinson, R.A. (2022), Methacrylate and Styrene Block Copolymer Synthesis by Cu-Mediated Chain Extension of Acrylate Macroinitiator in a Semibatch Reactor. Macromol. React. Eng. 2100043. https://doi.org/10.1002/mren.202100043
Publisher
Wiley