Selectively Deuterated Poly(ε-caprolactone)s: Synthesis and Isotope Effects on the Crystal Structures and Properties
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- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Zhejiang Univ. of Technology, Zhejiang (China)
- Univ. of South Carolina, Columbia, SC (United States)
Selective deuteration is an important tool for many analytical techniques including neutron scattering and spectroscopies. However, the availability of deuterated materials is limited because of the challenges in their synthesis. Here, we report the synthesis of partially and fully deuterated ε-caprolactone monomers and their corresponding polymers, poly(ε-caprolactone)s (PCLs), and the investigation of isotope effects on their crystalline structures and physical properties. Deuteration of PCLs leads to smaller crystal lattices and volumes compared to protiated PCL by the amount proportional to the deuteration levels. The linear trend suggests that volume isotope effect in PCL is primarily governed by the vibrations of C-D and C-H bonds. The large intra-chain contraction of deuterated PCLs compared to that of polyethylene reported in literature can be ascribed to the presence of polar ester groups in PCL. Deuterated PCLs also display lower melting temperatures than protiated PCL proportional to their deuteration levels because of weaker intermolecular interactions in deuterated polymers. FTIR spectroscopy, with support from density functional theory calculations, shows large red-shifts of the stretching and bending frequencies of C-D versus C-H bonds as dictated by their relative reduced masses √(13/7), and to a smaller degree for the C=O stretching frequency. This work is among the very few studies comparing the effects of partial versus full deuterations on the structures and properties in semi-crystalline polymers. These results are not only advancing our understandings of isotope effects in polymeric materials, but also providing an important avenue to design polymers with desirable properties.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Science (SC). National Energy Research Scientific Computing Center (NERSC); National Science Foundation (NSF); University of South Carolina
- Grant/Contract Number:
- AC05-00OR22725; AC02-06CH11357; AC02-05CH11231
- OSTI ID:
- 1489105
- Alternate ID(s):
- OSTI ID: 1493882
- Journal Information:
- Macromolecules, Vol. 51, Issue 22; ISSN 0024-9297
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε‐Caprolactone)
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journal | April 2019 |
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