Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε-Caprolactone)
Abstract
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 , 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 CD 2 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.more »
- Authors:
-
[1];
[2];
[3];
[2];
[2];
[7]
- 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
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
- 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
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science and Neutron Scattering Division
- 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
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (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. https://doi.org/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. https://doi.org/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 = {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 , 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 CD 2 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. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57 , 771–779},
doi = {10.1002/polb.24831},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 12,
volume = 57,
place = {United States},
year = {Mon Apr 15 00:00:00 EDT 2019},
month = {Mon Apr 15 00:00:00 EDT 2019}
}
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