Effect of Corona Block Length on the Structure and Chain Exchange Kinetics of Block Copolymer Micelles

Wang, En; Lu, Jie; Bates, Frank S.; Lodge, Timothy P.

doi:10.1021/acs.macromol.7b02732

Effect of Corona Block Length on the Structure and Chain Exchange Kinetics of Block Copolymer Micelles

Journal Article · Tue May 01 00:00:00 EDT 2018 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.7b02732· OSTI ID:1455243

^[1]; Lu, Jie ^[1]; ^[1]; ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)

The effect of corona block length on micelle structure and molecular chain exchange kinetics has been investigated for a series of dilute poly(styrene)-b-poly(ethylene-alt-propylene) (SEP) diblock copolymer micelles with constant PS core block length ($$\langle$$N_core$$\rangle$$ ≈ 255) but different PEP corona block lengths (($$\langle$$N_corona$$\rangle$$ = 256–2080), using a combination of dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and time-resolved small-angle neutron scattering (TR-SANS). Smaller core radii and aggregation numbers, but significantly thicker corona layers (proportional to N_corona^0.7), were observed with increasing corona block length. Furthermore, 2 orders of magnitude more rapid chain exchange was observed in SEP micelles with the longest corona block compared to the shortest. This effect is attributed to the entropic gain arising from the relief of corona chain stretching upon chain expulsion. We further extend a previous theoretical model by explicitly including a corona term associated with the entropy change in the chain exchange process, which successfully explains the influence of the corona blocks on chain exchange. Our results are in excellent agreement with simulation results of Li and Dormidontova but are apparently contradictory with Halperin and Alexander’s theory for hairy micelles and with experimental observations in two other systems that the exchange kinetics slow down with increasing corona block length. These discrepancies reveal unanticipated complexity regarding the role of the corona block in chain exchange.

View Accepted Manuscript (DOE)

Research Organization:: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1455243

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 10 Vol. 51; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Effect of Corona Block Length on the Structure and Chain Exchange Kinetics of Block Copolymer Micelles

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