Polyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-Eutectic Acid-Base Organocatalysts

Andere Basterretxea; Elena Gabirondo; Coralie Jehanno; Haijin Zhu; Irma Flores; Alejandro J. Müller; Agustin Etxeberria; David Mecerreyes; Olivier Coulembier; Haritz Sardon

doi:10.1021/acssuschemeng.8b05609

Polyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-Eutectic Acid-Base Organocatalysts

Andere Basterretxea, Elena Gabirondo, Coralie Jehanno, Haijin Zhu, Irma Flores, Alejandro J. Müller, Agustin Etxeberria, David Mecerreyes, Olivier Coulembier, Haritz Sardon^*

^*Corresponding author for this work

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

35 Scopus citations

Abstract

Polyethers constitute a well-established class of polymers covering a wide range of applications from industrial manufacturing to nanomedicine. Nevertheless, their industrial implementation is limited to short chain aliphatic polyethers such as polyethylene glycol (PEO or PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG) produced by the ring-opening polymerization of the corresponding cyclic ethers. Herein, we report a sustainable and scalable approach for the preparation of medium and long chain aliphatic polyethers by the melt self-polycondensation of aliphatic diols in the presence of non-eutectic acid-base mixtures as organocatalyst. These organocatalysts were prepared by forming stoichiometric and non-stoichiometric complexes of methanesulfonic acid (MSA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as confirmed by NMR spectroscopy and DFT calculations. The non-stoichiometric 2:1 and 3:1 MSA:TBD molar complexes showed superior thermal stability. These non-eutectic acid-base mixtures were tested in the bulk-self-condensation of 1,6-hexanediol leading to telechelic α,I-hydroxy-poly(oxyhexane). The optimized polymerization conditions involved the use of MSA:TBD (3:1) catalyst in a three-step polycondensation process at 130-180 and 200 °C, respectively. These conditions were applied to the synthesis of a wide range of aliphatic polyethers with a number of methylene units ranging from 6 to 12 units and molecular weights between 5000 and 22 000 g mol ^-1 . The aliphatic polyethers were highly semicrystalline with melting temperatures ranging from 55 to 85 °C. The synthesis approach was extended to the preparation of value-added copolymers from different length chain diols and different functionality, giving rise to different copolymer architectures from linear copolyethers to polyether thermosets. Altogether, this straightforward polymerization strategy enables access to medium-long chain and cross-linked aliphatic polyethers using easily prepared and recyclable organocatalysts.

Original language	English
Pages (from-to)	4103-4111
Number of pages	9
Journal	ACS Sustainable Chemistry and Engineering
Volume	7
Issue number	4
DOIs	https://doi.org/10.1021/acssuschemeng.8b05609
State	Published - 18 Feb 2019
Externally published	Yes

Keywords

Non-eutectic acid-base mixtures
Organocatalyst
Polycondensation
Polyether

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acssuschemeng.8b05609

Cite this

@article{aaeb14ad7c0b497381dcd8e835445378,

title = "Polyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-Eutectic Acid-Base Organocatalysts",

abstract = " Polyethers constitute a well-established class of polymers covering a wide range of applications from industrial manufacturing to nanomedicine. Nevertheless, their industrial implementation is limited to short chain aliphatic polyethers such as polyethylene glycol (PEO or PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG) produced by the ring-opening polymerization of the corresponding cyclic ethers. Herein, we report a sustainable and scalable approach for the preparation of medium and long chain aliphatic polyethers by the melt self-polycondensation of aliphatic diols in the presence of non-eutectic acid-base mixtures as organocatalyst. These organocatalysts were prepared by forming stoichiometric and non-stoichiometric complexes of methanesulfonic acid (MSA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as confirmed by NMR spectroscopy and DFT calculations. The non-stoichiometric 2:1 and 3:1 MSA:TBD molar complexes showed superior thermal stability. These non-eutectic acid-base mixtures were tested in the bulk-self-condensation of 1,6-hexanediol leading to telechelic α,I-hydroxy-poly(oxyhexane). The optimized polymerization conditions involved the use of MSA:TBD (3:1) catalyst in a three-step polycondensation process at 130-180 and 200 °C, respectively. These conditions were applied to the synthesis of a wide range of aliphatic polyethers with a number of methylene units ranging from 6 to 12 units and molecular weights between 5000 and 22 000 g mol -1 . The aliphatic polyethers were highly semicrystalline with melting temperatures ranging from 55 to 85 °C. The synthesis approach was extended to the preparation of value-added copolymers from different length chain diols and different functionality, giving rise to different copolymer architectures from linear copolyethers to polyether thermosets. Altogether, this straightforward polymerization strategy enables access to medium-long chain and cross-linked aliphatic polyethers using easily prepared and recyclable organocatalysts.",

keywords = "Non-eutectic acid-base mixtures, Organocatalyst, Polycondensation, Polyether",

author = "Andere Basterretxea and Elena Gabirondo and Coralie Jehanno and Haijin Zhu and Irma Flores and M{\"u}ller, {Alejandro J.} and Agustin Etxeberria and David Mecerreyes and Olivier Coulembier and Haritz Sardon",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = feb,

day = "18",

doi = "10.1021/acssuschemeng.8b05609",

language = "英语",

volume = "7",

pages = "4103--4111",

journal = "ACS Sustainable Chemistry and Engineering",

issn = "2168-0485",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Polyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-Eutectic Acid-Base Organocatalysts

AU - Basterretxea, Andere

AU - Gabirondo, Elena

AU - Jehanno, Coralie

AU - Zhu, Haijin

AU - Flores, Irma

AU - Müller, Alejandro J.

AU - Etxeberria, Agustin

AU - Mecerreyes, David

AU - Coulembier, Olivier

AU - Sardon, Haritz

PY - 2019/2/18

Y1 - 2019/2/18

N2 - Polyethers constitute a well-established class of polymers covering a wide range of applications from industrial manufacturing to nanomedicine. Nevertheless, their industrial implementation is limited to short chain aliphatic polyethers such as polyethylene glycol (PEO or PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG) produced by the ring-opening polymerization of the corresponding cyclic ethers. Herein, we report a sustainable and scalable approach for the preparation of medium and long chain aliphatic polyethers by the melt self-polycondensation of aliphatic diols in the presence of non-eutectic acid-base mixtures as organocatalyst. These organocatalysts were prepared by forming stoichiometric and non-stoichiometric complexes of methanesulfonic acid (MSA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as confirmed by NMR spectroscopy and DFT calculations. The non-stoichiometric 2:1 and 3:1 MSA:TBD molar complexes showed superior thermal stability. These non-eutectic acid-base mixtures were tested in the bulk-self-condensation of 1,6-hexanediol leading to telechelic α,I-hydroxy-poly(oxyhexane). The optimized polymerization conditions involved the use of MSA:TBD (3:1) catalyst in a three-step polycondensation process at 130-180 and 200 °C, respectively. These conditions were applied to the synthesis of a wide range of aliphatic polyethers with a number of methylene units ranging from 6 to 12 units and molecular weights between 5000 and 22 000 g mol -1 . The aliphatic polyethers were highly semicrystalline with melting temperatures ranging from 55 to 85 °C. The synthesis approach was extended to the preparation of value-added copolymers from different length chain diols and different functionality, giving rise to different copolymer architectures from linear copolyethers to polyether thermosets. Altogether, this straightforward polymerization strategy enables access to medium-long chain and cross-linked aliphatic polyethers using easily prepared and recyclable organocatalysts.

AB - Polyethers constitute a well-established class of polymers covering a wide range of applications from industrial manufacturing to nanomedicine. Nevertheless, their industrial implementation is limited to short chain aliphatic polyethers such as polyethylene glycol (PEO or PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG) produced by the ring-opening polymerization of the corresponding cyclic ethers. Herein, we report a sustainable and scalable approach for the preparation of medium and long chain aliphatic polyethers by the melt self-polycondensation of aliphatic diols in the presence of non-eutectic acid-base mixtures as organocatalyst. These organocatalysts were prepared by forming stoichiometric and non-stoichiometric complexes of methanesulfonic acid (MSA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as confirmed by NMR spectroscopy and DFT calculations. The non-stoichiometric 2:1 and 3:1 MSA:TBD molar complexes showed superior thermal stability. These non-eutectic acid-base mixtures were tested in the bulk-self-condensation of 1,6-hexanediol leading to telechelic α,I-hydroxy-poly(oxyhexane). The optimized polymerization conditions involved the use of MSA:TBD (3:1) catalyst in a three-step polycondensation process at 130-180 and 200 °C, respectively. These conditions were applied to the synthesis of a wide range of aliphatic polyethers with a number of methylene units ranging from 6 to 12 units and molecular weights between 5000 and 22 000 g mol -1 . The aliphatic polyethers were highly semicrystalline with melting temperatures ranging from 55 to 85 °C. The synthesis approach was extended to the preparation of value-added copolymers from different length chain diols and different functionality, giving rise to different copolymer architectures from linear copolyethers to polyether thermosets. Altogether, this straightforward polymerization strategy enables access to medium-long chain and cross-linked aliphatic polyethers using easily prepared and recyclable organocatalysts.

KW - Non-eutectic acid-base mixtures

KW - Organocatalyst

KW - Polycondensation

KW - Polyether

UR - http://www.scopus.com/inward/record.url?scp=85061527933&partnerID=8YFLogxK

U2 - 10.1021/acssuschemeng.8b05609

DO - 10.1021/acssuschemeng.8b05609

M3 - 文章

AN - SCOPUS:85061527933

SN - 2168-0485

VL - 7

SP - 4103

EP - 4111

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 4

ER -

Polyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-Eutectic Acid-Base Organocatalysts

Abstract

Keywords

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this