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Structural Evolution of Polylactide Molecular Bottlebrushes: Kinetics Study by Size Exclusion Chromatography, Small Angle Neutron Scattering, and Simulations

Journal Article · · ACS Macro Letters
DOI:https://doi.org/10.1021/mz5003454· OSTI ID:1265259
 [1];  [2];  [3];  [4];  [1];  [1];  [1];  [5];  [3];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biology and Soft Matter Divison
  4. Korea Atomic Energy Research Institute (Korea). Neutron Science Division, Department of Reactor Utilization and Development
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS), Computer Science and Mathematics Division
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In this paper, structural evolution from poly(lactide) (PLA) macromonomer to resultant PLA molecular bottlebrush during ring opening metathesis polymerization (ROMP) was investigated for the first time by combining size exclusion chromatography (SEC), small-angle neutron scattering (SANS), and coarse-grained molecular dynamics (CG-MD) simulations. Multiple aliquots were collected at various reaction times during ROMP and subsequently analyzed by SEC and SANS. These complementary techniques enable the understanding of systematic changes in conversion, molecular weight and dispersity as well as structural details of PLA molecular bottlebrushes. CG-MD simulation not only predicts the experimental observations, but it also provides further insight into the analysis and interpretation of data obtained in SEC and SANS experiments. Finally, we find that PLA molecular bottlebrushes undergo three conformational transitions with increasing conversion (i.e., increasing the backbone length): (1) from an elongated to a globular shape due to longer side chain at low conversion, (2) from a globular to an elongated shape at intermediate conversion caused by excluded volume of PLA side chain, and (3) the saturation of contour length at high conversion due to chain transfer reactions.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
AC05-00OR22725
OSTI ID:
1265259
Journal Information:
ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 9 Vol. 3; ISSN 2161-1653
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY