Synthesis, morphology and crystallization kinetics of Polyheptalactone (PHL)

Maria Caputo; Asier Olmos; Bo Li; Jorge L. Olmedo-Martínez; Anna Malafronte; Claudio De Rosa; Haritz Sardon; Rachel O'Reilly; Andrew Dove; Alejandro J. Müller

doi:10.1021/acs.biomac.3c00305

Synthesis, morphology and crystallization kinetics of Polyheptalactone (PHL)

Maria Caputo, Asier Olmos, Bo Li, Jorge L. Olmedo-Martínez, Anna Malafronte, Claudio De Rosa, Haritz Sardon, Rachel O'Reilly, Andrew Dove, Alejandro J. Müller^*

^*Corresponding author for this work

Chemistry

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Abstract

Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL). First, we synthesized the η-heptalactone monomer by the Baeyer–Villiger oxidation of cycloheptanone before several polyheptalactones of different molecular weights (in the range between 2 and 12 kDa), and low dispersities were prepared by ring-opening polymerization (ROP). The influence of molecular weight on primary nucleation rate, spherulitic growth rate, and overall crystallization rate was studied for the first time. All of these rates increased with PHL molecular weight, and they approached a plateau for the highest molecular weight samples employed here. Single crystals of PHLs were prepared for the first time, and hexagonal-shaped flat single crystals were obtained. The study of the crystallization and morphology of PHL revealed strong similarities with PCL, making PHLs very promising materials, considering their potential biodegradable character.

Original language	English
Pages (from-to)	3256–3267
Number of pages	12
Journal	Biomacromolecules
Volume	24
Issue number	7
DOIs	https://doi.org/10.1021/acs.biomac.3c00305
Publication status	Published - 21 Jun 2023

Bibliographical note

This work has received funding from the Basque Government through grant IT1503-22. The authors would also like to acknowledge the financial support from the BIODEST project; this project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 778092.

Keywords

aliphatic polyesters
biodegradable
polyheptalactone
ring-opening polymerization

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10.1021/acs.biomac.3c00305Licence: Creative Commons: Attribution (CC BY)

CaputoM2023SynthesisFinal published version, 10.7 MBLicence: Creative Commons: Attribution (CC BY)

H2020_RISE_BIODEST
Dove, A.
European Commission
1/01/18 → 31/12/22
Project: EU

Cite this

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title = "Synthesis, morphology and crystallization kinetics of Polyheptalactone (PHL)",

abstract = "Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL). First, we synthesized the η-heptalactone monomer by the Baeyer–Villiger oxidation of cycloheptanone before several polyheptalactones of different molecular weights (in the range between 2 and 12 kDa), and low dispersities were prepared by ring-opening polymerization (ROP). The influence of molecular weight on primary nucleation rate, spherulitic growth rate, and overall crystallization rate was studied for the first time. All of these rates increased with PHL molecular weight, and they approached a plateau for the highest molecular weight samples employed here. Single crystals of PHLs were prepared for the first time, and hexagonal-shaped flat single crystals were obtained. The study of the crystallization and morphology of PHL revealed strong similarities with PCL, making PHLs very promising materials, considering their potential biodegradable character.",

keywords = "aliphatic polyesters, biodegradable, polyheptalactone, ring-opening polymerization",

author = "Maria Caputo and Asier Olmos and Bo Li and Olmedo-Mart{\'i}nez, {Jorge L.} and Anna Malafronte and {De Rosa}, Claudio and Haritz Sardon and Rachel O'Reilly and Andrew Dove and M{\"u}ller, {Alejandro J.}",

note = "This work has received funding from the Basque Government through grant IT1503-22. The authors would also like to acknowledge the financial support from the BIODEST project; this project has received funding from the European Union{\textquoteright}s Horizon 2020 research and innovation program under the Marie Sk{\l}odowska-Curie grant agreement No. 778092.",

year = "2023",

month = jun,

day = "21",

doi = "10.1021/acs.biomac.3c00305",

language = "English",

volume = "24",

pages = "3256–3267",

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T1 - Synthesis, morphology and crystallization kinetics of Polyheptalactone (PHL)

AU - Caputo, Maria

AU - Olmos, Asier

AU - Li, Bo

AU - Olmedo-Martínez, Jorge L.

AU - Malafronte, Anna

AU - De Rosa, Claudio

AU - Sardon, Haritz

AU - O'Reilly, Rachel

AU - Dove, Andrew

AU - Müller, Alejandro J.

N1 - This work has received funding from the Basque Government through grant IT1503-22. The authors would also like to acknowledge the financial support from the BIODEST project; this project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 778092.

PY - 2023/6/21

Y1 - 2023/6/21

N2 - Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL). First, we synthesized the η-heptalactone monomer by the Baeyer–Villiger oxidation of cycloheptanone before several polyheptalactones of different molecular weights (in the range between 2 and 12 kDa), and low dispersities were prepared by ring-opening polymerization (ROP). The influence of molecular weight on primary nucleation rate, spherulitic growth rate, and overall crystallization rate was studied for the first time. All of these rates increased with PHL molecular weight, and they approached a plateau for the highest molecular weight samples employed here. Single crystals of PHLs were prepared for the first time, and hexagonal-shaped flat single crystals were obtained. The study of the crystallization and morphology of PHL revealed strong similarities with PCL, making PHLs very promising materials, considering their potential biodegradable character.

AB - Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL). First, we synthesized the η-heptalactone monomer by the Baeyer–Villiger oxidation of cycloheptanone before several polyheptalactones of different molecular weights (in the range between 2 and 12 kDa), and low dispersities were prepared by ring-opening polymerization (ROP). The influence of molecular weight on primary nucleation rate, spherulitic growth rate, and overall crystallization rate was studied for the first time. All of these rates increased with PHL molecular weight, and they approached a plateau for the highest molecular weight samples employed here. Single crystals of PHLs were prepared for the first time, and hexagonal-shaped flat single crystals were obtained. The study of the crystallization and morphology of PHL revealed strong similarities with PCL, making PHLs very promising materials, considering their potential biodegradable character.

KW - aliphatic polyesters

KW - biodegradable

KW - polyheptalactone

KW - ring-opening polymerization

U2 - 10.1021/acs.biomac.3c00305

DO - 10.1021/acs.biomac.3c00305

M3 - Article

SN - 1525-7797

VL - 24

SP - 3256

EP - 3267

JO - Biomacromolecules

JF - Biomacromolecules

IS - 7

ER -

Synthesis, morphology and crystallization kinetics of Polyheptalactone (PHL)

Abstract

Bibliographical note

Keywords

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H2020_RISE_BIODEST

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