Use of Non‐isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring‐Opening Polymerization of D‐lactide

Sawarot Phetsuk; Robert Molloy; Paul D. Topham; Brian J. Tighe; Puttinan Meepowpan; Wanich Limwanich; Winita Punyodom

doi:10.1002/pi.6517

Use of Non‐isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring‐Opening Polymerization of D‐lactide

Sawarot Phetsuk, Robert Molloy, Paul D. Topham, Brian J. Tighe, Puttinan Meepowpan, Wanich Limwanich, Winita Punyodom

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

Abstract

Understanding the kinetics and mechanism of polymerization, particularly the role of the catalyst or initiator used, allows for the manipulation and control of the fabrication of new materials by the most convenient, straightforward routes. The kinetics of the bulk ring-opening polymerization (ROP) of D-lactide, a useful monomer employed to control the properties of poly(L-lactide), have been studied herein to identify a relatively quick (1 h), controlled, yet convenient, route to moderately high molecular weight poly(D-lactide). Tin(II) octoate [Sn(Oct)2], Sn(Oct)2/n-butanol (nBuOH) and liquid tin(II) butoxide [Sn(OnBu)2] as initiating systems were investigated by non-isothermal differential scanning calorimetry (DSC). Isoconversional methods were employed to determine the activation energy (Ea) for each reaction. The results showed that liquid Sn(OnBu)2 was a more efficient initiator than the commonly reported initiating systems of Sn(Oct)2 and Sn(Oct)2/nBuOH in terms of producing higher polymerization rates and polymer molecular weights. High molecular weight Poly D-lactide (1.8×105 Da) with moderate dispersity (Ð 1.3) was obtained using 0.1 mol% liquid Sn(OnBu)2 as the initiator at 120 °C. This present work describes the applications of non-isothermal DSC and isoconversional methods in comparing the effectiveness of different initiators in the bulk ROP of D-lactide for the first time.

Original language	English
Journal	Polymer International
Early online date	25 Feb 2023
DOIs	https://doi.org/10.1002/pi.6517
Publication status	E-pub ahead of print - 25 Feb 2023

Bibliographical note

This is the peer reviewed version of the following article: Phetsuk, S. et al (2023), Use of Non-isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring-Opening Polymerization of D-lactide. Polym Int. Accepted Author Manuscript. Which has been published in final form at https://doi.org/10.1002/pi.6517. 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.

Keywords

Polymers and Plastics
Materials Chemistry
Organic Chemistry

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title = "Use of Non‐isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring‐Opening Polymerization of D‐lactide",

abstract = "Understanding the kinetics and mechanism of polymerization, particularly the role of the catalyst or initiator used, allows for the manipulation and control of the fabrication of new materials by the most convenient, straightforward routes. The kinetics of the bulk ring-opening polymerization (ROP) of D-lactide, a useful monomer employed to control the properties of poly(L-lactide), have been studied herein to identify a relatively quick (1 h), controlled, yet convenient, route to moderately high molecular weight poly(D-lactide). Tin(II) octoate [Sn(Oct)2], Sn(Oct)2/n-butanol (nBuOH) and liquid tin(II) butoxide [Sn(OnBu)2] as initiating systems were investigated by non-isothermal differential scanning calorimetry (DSC). Isoconversional methods were employed to determine the activation energy (Ea) for each reaction. The results showed that liquid Sn(OnBu)2 was a more efficient initiator than the commonly reported initiating systems of Sn(Oct)2 and Sn(Oct)2/nBuOH in terms of producing higher polymerization rates and polymer molecular weights. High molecular weight Poly D-lactide (1.8×105 Da) with moderate dispersity ({\DH} 1.3) was obtained using 0.1 mol% liquid Sn(OnBu)2 as the initiator at 120 °C. This present work describes the applications of non-isothermal DSC and isoconversional methods in comparing the effectiveness of different initiators in the bulk ROP of D-lactide for the first time.",

keywords = "Polymers and Plastics, Materials Chemistry, Organic Chemistry",

author = "Sawarot Phetsuk and Robert Molloy and Topham, {Paul D.} and Tighe, {Brian J.} and Puttinan Meepowpan and Wanich Limwanich and Winita Punyodom",

note = "This is the peer reviewed version of the following article: Phetsuk, S. et al (2023), Use of Non-isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring-Opening Polymerization of D-lactide. Polym Int. Accepted Author Manuscript. Which has been published in final form at https://doi.org/10.1002/pi.6517. 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{\textquoteright}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.",

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AU - Phetsuk, Sawarot

AU - Molloy, Robert

AU - Topham, Paul D.

AU - Tighe, Brian J.

AU - Meepowpan, Puttinan

AU - Limwanich, Wanich

AU - Punyodom, Winita

N1 - This is the peer reviewed version of the following article: Phetsuk, S. et al (2023), Use of Non-isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring-Opening Polymerization of D-lactide. Polym Int. Accepted Author Manuscript. Which has been published in final form at https://doi.org/10.1002/pi.6517. 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.

PY - 2023/2/25

Y1 - 2023/2/25

N2 - Understanding the kinetics and mechanism of polymerization, particularly the role of the catalyst or initiator used, allows for the manipulation and control of the fabrication of new materials by the most convenient, straightforward routes. The kinetics of the bulk ring-opening polymerization (ROP) of D-lactide, a useful monomer employed to control the properties of poly(L-lactide), have been studied herein to identify a relatively quick (1 h), controlled, yet convenient, route to moderately high molecular weight poly(D-lactide). Tin(II) octoate [Sn(Oct)2], Sn(Oct)2/n-butanol (nBuOH) and liquid tin(II) butoxide [Sn(OnBu)2] as initiating systems were investigated by non-isothermal differential scanning calorimetry (DSC). Isoconversional methods were employed to determine the activation energy (Ea) for each reaction. The results showed that liquid Sn(OnBu)2 was a more efficient initiator than the commonly reported initiating systems of Sn(Oct)2 and Sn(Oct)2/nBuOH in terms of producing higher polymerization rates and polymer molecular weights. High molecular weight Poly D-lactide (1.8×105 Da) with moderate dispersity (Ð 1.3) was obtained using 0.1 mol% liquid Sn(OnBu)2 as the initiator at 120 °C. This present work describes the applications of non-isothermal DSC and isoconversional methods in comparing the effectiveness of different initiators in the bulk ROP of D-lactide for the first time.

AB - Understanding the kinetics and mechanism of polymerization, particularly the role of the catalyst or initiator used, allows for the manipulation and control of the fabrication of new materials by the most convenient, straightforward routes. The kinetics of the bulk ring-opening polymerization (ROP) of D-lactide, a useful monomer employed to control the properties of poly(L-lactide), have been studied herein to identify a relatively quick (1 h), controlled, yet convenient, route to moderately high molecular weight poly(D-lactide). Tin(II) octoate [Sn(Oct)2], Sn(Oct)2/n-butanol (nBuOH) and liquid tin(II) butoxide [Sn(OnBu)2] as initiating systems were investigated by non-isothermal differential scanning calorimetry (DSC). Isoconversional methods were employed to determine the activation energy (Ea) for each reaction. The results showed that liquid Sn(OnBu)2 was a more efficient initiator than the commonly reported initiating systems of Sn(Oct)2 and Sn(Oct)2/nBuOH in terms of producing higher polymerization rates and polymer molecular weights. High molecular weight Poly D-lactide (1.8×105 Da) with moderate dispersity (Ð 1.3) was obtained using 0.1 mol% liquid Sn(OnBu)2 as the initiator at 120 °C. This present work describes the applications of non-isothermal DSC and isoconversional methods in comparing the effectiveness of different initiators in the bulk ROP of D-lactide for the first time.

KW - Polymers and Plastics

KW - Materials Chemistry

KW - Organic Chemistry

UR - https://onlinelibrary.wiley.com/doi/10.1002/pi.6517

U2 - 10.1002/pi.6517

DO - 10.1002/pi.6517

M3 - Article

JO - Polymer International

JF - Polymer International

SN - 0959-8103

ER -

Use of Non‐isothermal DSC in Comparative Studies of Tin(II) Systems for the Ring‐Opening Polymerization of D‐lactide

Abstract

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