Abstract
Recently, a variety of "click"or other additive chemistries have been introduced to functionalize polymers after polymerization to target specific applications, for example, membranes, catalysis, or drug delivery systems. It is generally assumed that the inclusion of these "click"linking groups has minimal impact on the thermodynamics of the polymer as a whole. In this study, we demonstrate that the introduction of these click-derived units has a profound impact on the Flory-Huggins parameter of polyether derivatives. Using random phase approximation fits for small-angle X-ray scattering data from block copolymer pairs to estimate the Flory-Huggins interaction parameter (χ), we determined that poly(ethylene oxide) (PEO) and poly(allyl glycidyl ether) (PAGE), which differ only by the inclusion of an allyl sidechain, have a χ of 0.030 (at T = 34 °C). While PEO is miscible with poly(lactide) (PLA) at nearly all temperatures, the PLA/PAGE χ determined experimentally is 0.015 (at T = 30 °C). Atomistic molecular dynamics simulations of PEO/PAGE oligomer blends show that upon blending, PEO chains contract and move closer together, while PAGE chains stretch and spread apart, indicating an enthalpic contribution to the χ parameter due to changes in polymer coordination resulting from the conformational asymmetry of PAGE and PEO. These studies demonstrate the large impact that functionalization and side-chain units have on the χ parameter of polymer pairs.
| Original language | English |
|---|---|
| Pages (from-to) | 6670-6677 |
| Number of pages | 8 |
| Journal | Macromolecules |
| Volume | 54 |
| Issue number | 14 |
| DOIs | |
| State | Published - Jul 27 2021 |
Bibliographical note
Publisher Copyright:© 2021 American Chemical Society. All rights reserved.
Funding
This work was supported as part of the Center for Materials for Water and Energy Systems, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award #DE-SC0019272. This research used resources at the National Synchrotron Light Source II (a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract DE-SC0012704) and the Advanced Light Source (a U.S. DOE Office of Science User Facility under Contract DE-AC02-05CH11231). We gratefully acknowledge the use of shared facilities of the NSF Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara, DMR-1720256. The UC Santa Barbara MRSEC is a member of the Materials Research Facilities Network. The results in this paper were generated using high-performance computing resources provided by The University of Texas at Austin Texas Advanced Computing Center. EZ gratefully acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant no. 000392968. The authors thank Dr. Rachel Behrens for help with polymer characterization, Drs. Masafumi Fukuto and Ruipeng Li for assistance with SAXS measurements, and Nicholas Sherck for his useful comments and discussion.
| Funders | Funder number |
|---|---|
| National Science Foundation (NSF) | 000392968 |
| Michigan State University-U.S. Department of Energy (MSU-DOE) Plant Research Laboratory | |
| Office of Science Programs | |
| Office of Basic Energy Sciences | -SC0019272 |
| Brookhaven National Laboratory (BNL) | DE-AC02-05CH11231, DE-SC0012704 |
ASJC Scopus subject areas
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry