Journal
MACROMOLECULES
Volume 54, Issue 14, Pages 6670-6677Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.1c00134
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Funding
- Center for Materials for Water and Energy Systems, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0019272]
- DOE Office of Science [DE-SC0012704]
- U.S. DOE Office of Science User Facility [DE-AC02-05CH11231]
- NSF Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara [DMR-1720256]
- National Science Foundation Graduate Research Fellowship [000392968]
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This study demonstrates that the introduction of click-derived units has a significant impact on the Flory-Huggins parameter of polyether derivatives, showing the important influence of functionalization and side-chain units on the chi parameter of polymer pairs.
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 (chi), 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 chi of 0.030 (at T = 34 degrees C). While PEO is miscible with poly(lactide) (PLA) at nearly all temperatures, the PLA/PAGE. determined experimentally is 0.015 (at T = 30 degrees 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 chi 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 chi parameter of polymer pairs.
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