Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine

Claire Nicole Brodie; Alister Stewart Goodfellow; Matthew Andrews; Aniekan Ekpenyong Owen; Michael Buehl; Amit Kumar

doi:10.1038/s41467-024-50403-z

Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine

Claire Nicole Brodie, Alister Stewart Goodfellow, Matthew Andrews, Aniekan Ekpenyong Owen, Michael Buehl^*, Amit Kumar^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

We report here a method to make a branched and partially ethoxylated polyethyleneimine derivative directly from ethanolamine. The polymerization reaction is catalysed by a pincer complex of Earth-abundant metal, manganese, and produces water as the only byproduct. Industrial processes to produce polyethyleneimines involve the transformation of ethanolamine to a highly toxic chemical, aziridine, by an energy-intensive/waste-generating process followed by the ring-opening polymerization of aziridine. The reported method bypasses the need to produce a highly toxic intermediate and presents advantages over the current state-of-the-art. We propose that the polymerization process follows a hydrogen borrowing pathway that involves (a) dehydrogenation of ethanolamine to form 2-aminoacetaldehyde, (b) dehydrative coupling of 2-aminoacetaldehyde with ethanolamine to form an imine derivative, and (c) subsequent hydrogenation of imine derivative to form alkylated amines.

Original language	English
Article number	6253
Number of pages	9
Journal	Nature Communications
Volume	15
DOIs	https://doi.org/10.1038/s41467-024-50403-z
Publication status	Published - 24 Jul 2024

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@article{adcecf6375ed41e5bd72845c6e023cb2,

title = "Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine",

abstract = "We report here a method to make a branched and partially ethoxylated polyethyleneimine derivative directly from ethanolamine. The polymerization reaction is catalysed by a pincer complex of Earth-abundant metal, manganese, and produces water as the only byproduct. Industrial processes to produce polyethyleneimines involve the transformation of ethanolamine to a highly toxic chemical, aziridine, by an energy-intensive/waste-generating process followed by the ring-opening polymerization of aziridine. The reported method bypasses the need to produce a highly toxic intermediate and presents advantages over the current state-of-the-art. We propose that the polymerization process follows a hydrogen borrowing pathway that involves (a) dehydrogenation of ethanolamine to form 2-aminoacetaldehyde, (b) dehydrative coupling of 2-aminoacetaldehyde with ethanolamine to form an imine derivative, and (c) subsequent hydrogenation of imine derivative to form alkylated amines.",

author = "Brodie, \{Claire Nicole\} and Goodfellow, \{Alister Stewart\} and Matthew Andrews and Owen, \{Aniekan Ekpenyong\} and Michael Buehl and Amit Kumar",

note = "Funding: This research is funded by a UKRI Future Leaders Fellowship (MR/W007460/1) and the EaSI- CAT centre for Doctoral Training (A.S.G.). M.B. wishes to thank the School of Chemistry and EaStCHEM for their support. A.E.O. gratefully acknowledges a fellowship from the Akwa Ibom State University (TETFund). ",

year = "2024",

month = jul,

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doi = "10.1038/s41467-024-50403-z",

language = "English",

volume = "15",

journal = "Nature Communications",

issn = "2041-1723",

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TY - JOUR

T1 - Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine

AU - Brodie, Claire Nicole

AU - Goodfellow, Alister Stewart

AU - Andrews, Matthew

AU - Owen, Aniekan Ekpenyong

AU - Buehl, Michael

AU - Kumar, Amit

N1 - Funding: This research is funded by a UKRI Future Leaders Fellowship (MR/W007460/1) and the EaSI- CAT centre for Doctoral Training (A.S.G.). M.B. wishes to thank the School of Chemistry and EaStCHEM for their support. A.E.O. gratefully acknowledges a fellowship from the Akwa Ibom State University (TETFund).

PY - 2024/7/24

Y1 - 2024/7/24

N2 - We report here a method to make a branched and partially ethoxylated polyethyleneimine derivative directly from ethanolamine. The polymerization reaction is catalysed by a pincer complex of Earth-abundant metal, manganese, and produces water as the only byproduct. Industrial processes to produce polyethyleneimines involve the transformation of ethanolamine to a highly toxic chemical, aziridine, by an energy-intensive/waste-generating process followed by the ring-opening polymerization of aziridine. The reported method bypasses the need to produce a highly toxic intermediate and presents advantages over the current state-of-the-art. We propose that the polymerization process follows a hydrogen borrowing pathway that involves (a) dehydrogenation of ethanolamine to form 2-aminoacetaldehyde, (b) dehydrative coupling of 2-aminoacetaldehyde with ethanolamine to form an imine derivative, and (c) subsequent hydrogenation of imine derivative to form alkylated amines.

AB - We report here a method to make a branched and partially ethoxylated polyethyleneimine derivative directly from ethanolamine. The polymerization reaction is catalysed by a pincer complex of Earth-abundant metal, manganese, and produces water as the only byproduct. Industrial processes to produce polyethyleneimines involve the transformation of ethanolamine to a highly toxic chemical, aziridine, by an energy-intensive/waste-generating process followed by the ring-opening polymerization of aziridine. The reported method bypasses the need to produce a highly toxic intermediate and presents advantages over the current state-of-the-art. We propose that the polymerization process follows a hydrogen borrowing pathway that involves (a) dehydrogenation of ethanolamine to form 2-aminoacetaldehyde, (b) dehydrative coupling of 2-aminoacetaldehyde with ethanolamine to form an imine derivative, and (c) subsequent hydrogenation of imine derivative to form alkylated amines.

UR - https://doi.org/10.26434/chemrxiv-2023-m16q0

UR - https://www.scopus.com/pages/publications/85199662785

U2 - 10.1038/s41467-024-50403-z

DO - 10.1038/s41467-024-50403-z

M3 - Article

SN - 2041-1723

VL - 15

JO - Nature Communications

JF - Nature Communications

M1 - 6253

ER -

Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine

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New Directions for the Sythesis: New Directions for the Synthesis and Degradation of Renewable and Recyclable Plastics Using Homogeneous Catalytic (De)hydrogenation