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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 $$T^{0}_{m}$$, 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [4];  [5]; ORCiD logo [2];  [6]; ORCiD logo [7]
  1. South China Univ. of Technology, Guangzhou (China). The Key Lab. of Polymer Processing Engineering of Ministry of Education; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science and Neutron Scattering Division
  6. South China Univ. of Technology, Guangzhou (China). The Key Lab. of Polymer Processing Engineering of Ministry of Education;
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1550757
Alternate Identifier(s):
OSTI ID: 1507187
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part B, Polymer Physics
Additional Journal Information:
Journal Volume: 57; Journal Issue: 12; Journal ID: ISSN 0887-6266
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; crystallization kinetics; deuterated poly(ε-caprolactone); hydrogen bond; selectively deuteration sites

Citation Formats

Li, Lengwan, Chang, Dongsook, Arras, Matthias M. L., Li, Wei, Li, Tianyu, Keum, Jong K., Bonnesen, Peter V., Peng, Xiangfang, and Hong, Kunlun. Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone). United States: N. p., 2019. Web. doi:10.1002/polb.24831.
Li, Lengwan, Chang, Dongsook, Arras, Matthias M. L., Li, Wei, Li, Tianyu, Keum, Jong K., Bonnesen, Peter V., Peng, Xiangfang, & Hong, Kunlun. Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone). United States. doi:10.1002/polb.24831.
Li, Lengwan, Chang, Dongsook, Arras, Matthias M. L., Li, Wei, Li, Tianyu, Keum, Jong K., Bonnesen, Peter V., Peng, Xiangfang, and Hong, Kunlun. Mon . "Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)". United States. doi:10.1002/polb.24831. https://www.osti.gov/servlets/purl/1550757.
@article{osti_1550757,
title = {Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)},
author = {Li, Lengwan and Chang, Dongsook and Arras, Matthias M. L. and Li, Wei and Li, Tianyu and Keum, Jong K. and Bonnesen, Peter V. and Peng, Xiangfang and Hong, Kunlun},
abstractNote = {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 $T^{0}_{m}$, 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.},
doi = {10.1002/polb.24831},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 12,
volume = 57,
place = {United States},
year = {2019},
month = {4}
}

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