Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)

Lengwan Li; Dongsook Chang; Matthias M.L. Arras; Wei Li; Tianyu Li; Jong K. Keum; Peter V. Bonnesen; Xiangfang Peng; Kunlun Hong

doi:10.1002/polb.24831

Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)

Lengwan Li, Dongsook Chang, Matthias M.L. Arras, Wei Li, Tianyu Li, Jong K. Keum, Peter V. Bonnesen, Xiangfang Peng, Kunlun Hong

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

10 Scopus citations

Abstract

Deuterium labeling of semi-crystalline polymers can dramatically affect their crystallization behaviors. However, the influence of different labeled positions in a partially deuterated polymer on its crystallization is still far from understood. Here, we synthesized a series of selectively deuterated poly(ε-caprolactones) (PCLs) through ring-opening polymerization of ε-caprolactone with controlled deuteration sites, including fully protiated (D0), fully deuterated (D10), tetra deuteration at the 3- and 7- caprolactone ring positions (D4) and hexa deuteration at the 4-, 5-, and 6- caprolactone ring positions (D6). All the PCLs showed a similar lamellar structure and parameters. Differential scanning calorimetry (DSC) analysis revealed that the equilibrium melting temperature (Formula presented.), melting temperature T_m, crystallization temperature T_c, and crystallization kinetics changed systemically with the deuterium content except for D4, which indicates that the presence of CD₂ moieties on either side of ester group in the polymer chain combined with isotopic inhomogeneity could influence the chain packing. The nonmonotonic trend of T_m as a function of deuterium content could be attributed to the difference in a hydrogen-bond like intermolecular interaction between different PCLs. Partially deuterated PCLs (D4 and D6) showed an Avrami index near 2. After analyzing the parameters at the same supercooling temperature ΔT_c, the existence of two crystallization regimes of PCLs were detected.

Original language	English
Pages (from-to)	771-779
Number of pages	9
Journal	Journal of Polymer Science, Part B: Polymer Physics
Volume	57
Issue number	12
DOIs	https://doi.org/10.1002/polb.24831
State	Published - Jun 15 2019

Funding

The authors gratefully appreciate the support of the National Natural Science Foundation of China (No. 51573063). L. Li thanks the Chinese Scholarship Council for its financial support. The polymers were synthesized and characterized at the Center for Nanophase Materials Sciences (CNMS) at the Oak Ridge National Laboratory (ORNL), which is a DOE Office of Science User Facility. Neutron scattering studies were performed at the CG-3 Bio-SANS instrument at the High-Flux Isotope Reactor (HFIR), ORNL, which is sponsored by the Office of Biological and Environmental Research, and the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. We thank Dr. Jingsong Huang, Dr. Jacek Jakowski, and Dr. Monojoy Goswami (Computational Sciences and Engineering Division, ORNL) for helping with the theoretical analysis.

Funders	Funder number
Chinese Scholarship Council
DOE Office of Science user facility
Office of Basic Energy Sciences
Office of Biological and Environmental Research
Scientific User Facilities Division
U.S. Department of Energy
Oak Ridge National Laboratory	ORNL
National Natural Science Foundation of China	51573063

Keywords

crystallization kinetics
deuterated poly(ε-caprolactone)
hydrogen bond
selectively deuteration sites

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10.1002/polb.24831

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title = "Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)",

abstract = "Deuterium labeling of semi-crystalline polymers can dramatically affect their crystallization behaviors. However, the influence of different labeled positions in a partially deuterated polymer on its crystallization is still far from understood. Here, we synthesized a series of selectively deuterated poly(ε-caprolactones) (PCLs) through ring-opening polymerization of ε-caprolactone with controlled deuteration sites, including fully protiated (D0), fully deuterated (D10), tetra deuteration at the 3- and 7- caprolactone ring positions (D4) and hexa deuteration at the 4-, 5-, and 6- caprolactone ring positions (D6). All the PCLs showed a similar lamellar structure and parameters. Differential scanning calorimetry (DSC) analysis revealed that the equilibrium melting temperature (Formula presented.), melting temperature Tm, crystallization temperature Tc, and crystallization kinetics changed systemically with the deuterium content except for D4, which indicates that the presence of CD2 moieties on either side of ester group in the polymer chain combined with isotopic inhomogeneity could influence the chain packing. The nonmonotonic trend of Tm as a function of deuterium content could be attributed to the difference in a hydrogen-bond like intermolecular interaction between different PCLs. Partially deuterated PCLs (D4 and D6) showed an Avrami index near 2. After analyzing the parameters at the same supercooling temperature ΔTc, the existence of two crystallization regimes of PCLs were detected.",

keywords = "crystallization kinetics, deuterated poly(ε-caprolactone), hydrogen bond, selectively deuteration sites",

author = "Lengwan Li and Dongsook Chang and Arras, {Matthias M.L.} and Wei Li and Tianyu Li and Keum, {Jong K.} and Bonnesen, {Peter V.} and Xiangfang Peng and Kunlun Hong",

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AU - Li, Lengwan

AU - Chang, Dongsook

AU - Arras, Matthias M.L.

AU - Li, Wei

AU - Li, Tianyu

AU - Keum, Jong K.

AU - Bonnesen, Peter V.

AU - Peng, Xiangfang

AU - Hong, Kunlun

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N2 - Deuterium labeling of semi-crystalline polymers can dramatically affect their crystallization behaviors. However, the influence of different labeled positions in a partially deuterated polymer on its crystallization is still far from understood. Here, we synthesized a series of selectively deuterated poly(ε-caprolactones) (PCLs) through ring-opening polymerization of ε-caprolactone with controlled deuteration sites, including fully protiated (D0), fully deuterated (D10), tetra deuteration at the 3- and 7- caprolactone ring positions (D4) and hexa deuteration at the 4-, 5-, and 6- caprolactone ring positions (D6). All the PCLs showed a similar lamellar structure and parameters. Differential scanning calorimetry (DSC) analysis revealed that the equilibrium melting temperature (Formula presented.), melting temperature Tm, crystallization temperature Tc, and crystallization kinetics changed systemically with the deuterium content except for D4, which indicates that the presence of CD2 moieties on either side of ester group in the polymer chain combined with isotopic inhomogeneity could influence the chain packing. The nonmonotonic trend of Tm as a function of deuterium content could be attributed to the difference in a hydrogen-bond like intermolecular interaction between different PCLs. Partially deuterated PCLs (D4 and D6) showed an Avrami index near 2. After analyzing the parameters at the same supercooling temperature ΔTc, the existence of two crystallization regimes of PCLs were detected.

AB - Deuterium labeling of semi-crystalline polymers can dramatically affect their crystallization behaviors. However, the influence of different labeled positions in a partially deuterated polymer on its crystallization is still far from understood. Here, we synthesized a series of selectively deuterated poly(ε-caprolactones) (PCLs) through ring-opening polymerization of ε-caprolactone with controlled deuteration sites, including fully protiated (D0), fully deuterated (D10), tetra deuteration at the 3- and 7- caprolactone ring positions (D4) and hexa deuteration at the 4-, 5-, and 6- caprolactone ring positions (D6). All the PCLs showed a similar lamellar structure and parameters. Differential scanning calorimetry (DSC) analysis revealed that the equilibrium melting temperature (Formula presented.), melting temperature Tm, crystallization temperature Tc, and crystallization kinetics changed systemically with the deuterium content except for D4, which indicates that the presence of CD2 moieties on either side of ester group in the polymer chain combined with isotopic inhomogeneity could influence the chain packing. The nonmonotonic trend of Tm as a function of deuterium content could be attributed to the difference in a hydrogen-bond like intermolecular interaction between different PCLs. Partially deuterated PCLs (D4 and D6) showed an Avrami index near 2. After analyzing the parameters at the same supercooling temperature ΔTc, the existence of two crystallization regimes of PCLs were detected.

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ER -

Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)

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