Water-soluble polyphosphonate-based bottlebrush copolymers via aqueous ring-opening metathesis polymerization

Diego A. Resendiz-Lara; Suna Azhdari; Hubert Gojzewski; Andre H. Gröschel; Frederik R. Wurm

doi:10.1039/d3sc02649c

Water-soluble polyphosphonate-based bottlebrush copolymers via aqueous ring-opening metathesis polymerization

Diego A. Resendiz-Lara, Suna Azhdari, Hubert Gojzewski, Andre H. Gröschel, Frederik R. Wurm^*

^*Corresponding author for this work

Sustainable Polymer Chemistry

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Abstract

Ring-opening metathesis polymerization (ROMP) is a versatile method for synthesizing complex macromolecules from various functional monomers. In this work, we report the synthesis of water-soluble and degradable bottlebrush polymers, based on polyphosphoesters (PPEs) via ROMP. First, PPE-macromonomers were synthesized via organocatalytic anionic ring-opening polymerization of 2-ethyl-2-oxo-1,3,2-dioxaphospholane using N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide as the initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the catalyst. The resulting norbornene-based macromonomers had degrees of polymerization (DP_n) ranging from 25 to 243 and narrow molar mass dispersity (Đ ≤ 1.10). Subsequently, these macromonomers were used in ROMP with the Grubbs 3^rd-generation bispyridyl complex (Ru-G3) to produce a library of well-defined bottlebrush polymers. The ROMP was carried out either in dioxane or in aqueous conditions, resulting in well-defined and water-soluble bottlebrush PPEs. Furthermore, a two-step protocol was employed to synthesize double hydrophilic diblock bottlebrush copolymers via ROMP in water at neutral pH-values. This general protocol enabled the direct combination of PPEs with ROMP to synthesize well-defined bottlebrush polymers and block copolymers in water. Degradation of the PPE side chains was proven resulting in low molar mass degradation products only. The biocompatible and biodegradable nature of PPEs makes this pathway promising for designing novel biomedical drug carriers or viscosity modifiers, as well as many other potential applications.

Original language	English
Pages (from-to)	11273-11282
Number of pages	10
Journal	Chemical science
Volume	14
Issue number	40
Early online date	26 Sept 2023
DOIs	https://doi.org/10.1039/d3sc02649c
Publication status	Published - 18 Oct 2023

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10.1039/d3sc02649cLicence: CC BY

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@article{f0db8daf9bc0426493de998e2ae53ec1,

title = "Water-soluble polyphosphonate-based bottlebrush copolymers via aqueous ring-opening metathesis polymerization",

abstract = "Ring-opening metathesis polymerization (ROMP) is a versatile method for synthesizing complex macromolecules from various functional monomers. In this work, we report the synthesis of water-soluble and degradable bottlebrush polymers, based on polyphosphoesters (PPEs) via ROMP. First, PPE-macromonomers were synthesized via organocatalytic anionic ring-opening polymerization of 2-ethyl-2-oxo-1,3,2-dioxaphospholane using N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide as the initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the catalyst. The resulting norbornene-based macromonomers had degrees of polymerization (DPn) ranging from 25 to 243 and narrow molar mass dispersity ({\D} ≤ 1.10). Subsequently, these macromonomers were used in ROMP with the Grubbs 3rd-generation bispyridyl complex (Ru-G3) to produce a library of well-defined bottlebrush polymers. The ROMP was carried out either in dioxane or in aqueous conditions, resulting in well-defined and water-soluble bottlebrush PPEs. Furthermore, a two-step protocol was employed to synthesize double hydrophilic diblock bottlebrush copolymers via ROMP in water at neutral pH-values. This general protocol enabled the direct combination of PPEs with ROMP to synthesize well-defined bottlebrush polymers and block copolymers in water. Degradation of the PPE side chains was proven resulting in low molar mass degradation products only. The biocompatible and biodegradable nature of PPEs makes this pathway promising for designing novel biomedical drug carriers or viscosity modifiers, as well as many other potential applications.",

author = "Resendiz-Lara, {Diego A.} and Suna Azhdari and Hubert Gojzewski and Gr{\"o}schel, {Andre H.} and Wurm, {Frederik R.}",

note = "Funding Information: The authors acknowledge the University of Twente (UT)–Westf{\"a}lische Wilhelms-Universit{\"a}t M{\"u}nster (WWU) Strategic Collaboration Grant 2021–2022 for financial support. The authors also acknowledge Ramon ten Elshof (UT) and Clemens J. Padberg (UT) for synthetic support and SEC experiments. Funding Information: The authors acknowledge the University of Twente (UT)-Westf{\"a}lische Wilhelms-Universit{\"a}t M{\"u}nster (WWU) Strategic Collaboration Grant 2021-2022 for financial support. The authors also acknowledge Ramon ten Elshof (UT) and Clemens J. Padberg (UT) for synthetic support and SEC experiments. Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

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doi = "10.1039/d3sc02649c",

language = "English",

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T1 - Water-soluble polyphosphonate-based bottlebrush copolymers via aqueous ring-opening metathesis polymerization

AU - Resendiz-Lara, Diego A.

AU - Azhdari, Suna

AU - Gojzewski, Hubert

AU - Gröschel, Andre H.

AU - Wurm, Frederik R.

N1 - Funding Information: The authors acknowledge the University of Twente (UT)–Westfälische Wilhelms-Universität Münster (WWU) Strategic Collaboration Grant 2021–2022 for financial support. The authors also acknowledge Ramon ten Elshof (UT) and Clemens J. Padberg (UT) for synthetic support and SEC experiments. Funding Information: The authors acknowledge the University of Twente (UT)-Westfälische Wilhelms-Universität Münster (WWU) Strategic Collaboration Grant 2021-2022 for financial support. The authors also acknowledge Ramon ten Elshof (UT) and Clemens J. Padberg (UT) for synthetic support and SEC experiments. Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023/10/18

Y1 - 2023/10/18

N2 - Ring-opening metathesis polymerization (ROMP) is a versatile method for synthesizing complex macromolecules from various functional monomers. In this work, we report the synthesis of water-soluble and degradable bottlebrush polymers, based on polyphosphoesters (PPEs) via ROMP. First, PPE-macromonomers were synthesized via organocatalytic anionic ring-opening polymerization of 2-ethyl-2-oxo-1,3,2-dioxaphospholane using N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide as the initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the catalyst. The resulting norbornene-based macromonomers had degrees of polymerization (DPn) ranging from 25 to 243 and narrow molar mass dispersity (Đ ≤ 1.10). Subsequently, these macromonomers were used in ROMP with the Grubbs 3rd-generation bispyridyl complex (Ru-G3) to produce a library of well-defined bottlebrush polymers. The ROMP was carried out either in dioxane or in aqueous conditions, resulting in well-defined and water-soluble bottlebrush PPEs. Furthermore, a two-step protocol was employed to synthesize double hydrophilic diblock bottlebrush copolymers via ROMP in water at neutral pH-values. This general protocol enabled the direct combination of PPEs with ROMP to synthesize well-defined bottlebrush polymers and block copolymers in water. Degradation of the PPE side chains was proven resulting in low molar mass degradation products only. The biocompatible and biodegradable nature of PPEs makes this pathway promising for designing novel biomedical drug carriers or viscosity modifiers, as well as many other potential applications.

AB - Ring-opening metathesis polymerization (ROMP) is a versatile method for synthesizing complex macromolecules from various functional monomers. In this work, we report the synthesis of water-soluble and degradable bottlebrush polymers, based on polyphosphoesters (PPEs) via ROMP. First, PPE-macromonomers were synthesized via organocatalytic anionic ring-opening polymerization of 2-ethyl-2-oxo-1,3,2-dioxaphospholane using N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide as the initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the catalyst. The resulting norbornene-based macromonomers had degrees of polymerization (DPn) ranging from 25 to 243 and narrow molar mass dispersity (Đ ≤ 1.10). Subsequently, these macromonomers were used in ROMP with the Grubbs 3rd-generation bispyridyl complex (Ru-G3) to produce a library of well-defined bottlebrush polymers. The ROMP was carried out either in dioxane or in aqueous conditions, resulting in well-defined and water-soluble bottlebrush PPEs. Furthermore, a two-step protocol was employed to synthesize double hydrophilic diblock bottlebrush copolymers via ROMP in water at neutral pH-values. This general protocol enabled the direct combination of PPEs with ROMP to synthesize well-defined bottlebrush polymers and block copolymers in water. Degradation of the PPE side chains was proven resulting in low molar mass degradation products only. The biocompatible and biodegradable nature of PPEs makes this pathway promising for designing novel biomedical drug carriers or viscosity modifiers, as well as many other potential applications.

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ER -

Water-soluble polyphosphonate-based bottlebrush copolymers via aqueous ring-opening metathesis polymerization

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