Investigation of monomer reactivity, polymer microstructure and solubility in the copolymerization of 1,5-dioxepan-2-one with alkyl substituted lactones

Jules Stouten; Marie A.F. Delgove; Nils De Vos; Kamiel Matthyssen; Geert G.P. Deroover; Katrien V. Bernaerts

doi:10.1016/j.eurpolymj.2023.112523

Investigation of monomer reactivity, polymer microstructure and solubility in the copolymerization of 1,5-dioxepan-2-one with alkyl substituted lactones

Jules Stouten, Marie A.F. Delgove, Nils De Vos, Kamiel Matthyssen, Geert G.P. Deroover, Katrien V. Bernaerts^*

^*Corresponding author for this work

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

Abstract

Ring Opening Polymerization of lactones is an excellent synthetic tool for the production of polyesters with tuned microstructure. In copolyesters, the polymer microstructure is an important feature that can greatly influence the properties. Therefore, it is desirable to investigate the copolymerization behaviour of monomers. In this work, the copolymerization of 1,5-dioxepan-2-one (DXP) with the potentially renewable alkyl substituted lactones d-undecalactone (UDL) and ß,d-trimethyl-e-caprolactone (TMCL) was investigated. The reactivity ratios were determined for both monomer pairs, and revealed that both substituted lactones react significantly different with DXP. Furthermore, the microstructure of copolymers from DXP and UDL with different monomer feed ratios was characterized by quantitative 13C NMR and MALDI-ToF MS analysis. The resulting copolymers exhibited a varying degree of randomness depending on the monomer feed ratio. The lactones in this study were selected for their different solubility properties. The Hansen solubility spheres were determined for the homo-and copolymers of DXP and UDL. Using this, we demonstrated that the polymer solubility properties can be tuned by copolymerization of polar and apolar monomers.

Original language	English
Article number	112523
Number of pages	9
Journal	European Polymer Journal
Volume	200
DOIs	https://doi.org/10.1016/j.eurpolymj.2023.112523
Publication status	Published - 22 Nov 2023

Keywords

Hansen solubility
Lactone
Microstructure
Reactivity ratios
Ring-opening polymerization

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10.1016/j.eurpolymj.2023.112523Licence: CC BY

Cite this

@article{a8fcfb5d4ca84107bf69dfdadaa9791a,

title = "Investigation of monomer reactivity, polymer microstructure and solubility in the copolymerization of 1,5-dioxepan-2-one with alkyl substituted lactones",

abstract = "Ring Opening Polymerization of lactones is an excellent synthetic tool for the production of polyesters with tuned microstructure. In copolyesters, the polymer microstructure is an important feature that can greatly influence the properties. Therefore, it is desirable to investigate the copolymerization behaviour of monomers. In this work, the copolymerization of 1,5-dioxepan-2-one (DXP) with the potentially renewable alkyl substituted lactones d-undecalactone (UDL) and {\ss},d-trimethyl-e-caprolactone (TMCL) was investigated. The reactivity ratios were determined for both monomer pairs, and revealed that both substituted lactones react significantly different with DXP. Furthermore, the microstructure of copolymers from DXP and UDL with different monomer feed ratios was characterized by quantitative 13C NMR and MALDI-ToF MS analysis. The resulting copolymers exhibited a varying degree of randomness depending on the monomer feed ratio. The lactones in this study were selected for their different solubility properties. The Hansen solubility spheres were determined for the homo-and copolymers of DXP and UDL. Using this, we demonstrated that the polymer solubility properties can be tuned by copolymerization of polar and apolar monomers.",

keywords = "Hansen solubility, Lactone, Microstructure, Reactivity ratios, Ring-opening polymerization",

author = "Jules Stouten and Delgove, {Marie A.F.} and {De Vos}, Nils and Kamiel Matthyssen and Deroover, {Geert G.P.} and Bernaerts, {Katrien V.}",

note = "Funding Information: The research for this work has received funding from the European Union (EU) project ROBOX (grant agreement n° 635734) under EU{\textquoteright}s Horizon 2020 Programme Research and Innovation actions H2020-LEIT BIO-2014-1. The views and opinions expressed in this article are only those of the authors, and do not necessarily reflect those of the European Union Research Agency. Funding Information: The research for this work has received funding from the European Union (EU) project ROBOX (grant agreement n° 635734) under EU's Horizon 2020 Programme Research and Innovation actions H2020-LEIT BIO-2014-1. The views and opinions expressed in this article are only those of the authors, and do not necessarily reflect those of the European Union Research Agency. Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = nov,

day = "22",

doi = "10.1016/j.eurpolymj.2023.112523",

language = "English",

volume = "200",

journal = "European Polymer Journal",

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T1 - Investigation of monomer reactivity, polymer microstructure and solubility in the copolymerization of 1,5-dioxepan-2-one with alkyl substituted lactones

AU - Stouten, Jules

AU - Delgove, Marie A.F.

AU - De Vos, Nils

AU - Matthyssen, Kamiel

AU - Deroover, Geert G.P.

AU - Bernaerts, Katrien V.

N1 - Funding Information: The research for this work has received funding from the European Union (EU) project ROBOX (grant agreement n° 635734) under EU’s Horizon 2020 Programme Research and Innovation actions H2020-LEIT BIO-2014-1. The views and opinions expressed in this article are only those of the authors, and do not necessarily reflect those of the European Union Research Agency. Funding Information: The research for this work has received funding from the European Union (EU) project ROBOX (grant agreement n° 635734) under EU's Horizon 2020 Programme Research and Innovation actions H2020-LEIT BIO-2014-1. The views and opinions expressed in this article are only those of the authors, and do not necessarily reflect those of the European Union Research Agency. Publisher Copyright: © 2023 The Author(s)

PY - 2023/11/22

Y1 - 2023/11/22

N2 - Ring Opening Polymerization of lactones is an excellent synthetic tool for the production of polyesters with tuned microstructure. In copolyesters, the polymer microstructure is an important feature that can greatly influence the properties. Therefore, it is desirable to investigate the copolymerization behaviour of monomers. In this work, the copolymerization of 1,5-dioxepan-2-one (DXP) with the potentially renewable alkyl substituted lactones d-undecalactone (UDL) and ß,d-trimethyl-e-caprolactone (TMCL) was investigated. The reactivity ratios were determined for both monomer pairs, and revealed that both substituted lactones react significantly different with DXP. Furthermore, the microstructure of copolymers from DXP and UDL with different monomer feed ratios was characterized by quantitative 13C NMR and MALDI-ToF MS analysis. The resulting copolymers exhibited a varying degree of randomness depending on the monomer feed ratio. The lactones in this study were selected for their different solubility properties. The Hansen solubility spheres were determined for the homo-and copolymers of DXP and UDL. Using this, we demonstrated that the polymer solubility properties can be tuned by copolymerization of polar and apolar monomers.

AB - Ring Opening Polymerization of lactones is an excellent synthetic tool for the production of polyesters with tuned microstructure. In copolyesters, the polymer microstructure is an important feature that can greatly influence the properties. Therefore, it is desirable to investigate the copolymerization behaviour of monomers. In this work, the copolymerization of 1,5-dioxepan-2-one (DXP) with the potentially renewable alkyl substituted lactones d-undecalactone (UDL) and ß,d-trimethyl-e-caprolactone (TMCL) was investigated. The reactivity ratios were determined for both monomer pairs, and revealed that both substituted lactones react significantly different with DXP. Furthermore, the microstructure of copolymers from DXP and UDL with different monomer feed ratios was characterized by quantitative 13C NMR and MALDI-ToF MS analysis. The resulting copolymers exhibited a varying degree of randomness depending on the monomer feed ratio. The lactones in this study were selected for their different solubility properties. The Hansen solubility spheres were determined for the homo-and copolymers of DXP and UDL. Using this, we demonstrated that the polymer solubility properties can be tuned by copolymerization of polar and apolar monomers.

KW - Hansen solubility

KW - Lactone

KW - Microstructure

KW - Reactivity ratios

KW - Ring-opening polymerization

U2 - 10.1016/j.eurpolymj.2023.112523

DO - 10.1016/j.eurpolymj.2023.112523

M3 - Article

SN - 0014-3057

VL - 200

JO - European Polymer Journal

JF - European Polymer Journal

M1 - 112523

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