How Does the Rate of Chain Exchange Relate to Stress Relaxation in Triblock Copolymer Networks?

White, Joanna M.; Kim, Taehyoung; Bates, Frank S.; Lodge, Timothy P.

doi:10.1021/acscentsci.4c02031

Title: How Does the Rate of Chain Exchange Relate to Stress Relaxation in Triblock Copolymer Networks?

Journal Article · Thu Feb 20 00:00:00 UTC 2025 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.4c02031 · OSTI ID:2520571

^[1]; Kim, Taehyoung ^[1];

^[1];

^[1]

University of Minnesota, Minneapolis, MN (United States)

The relationship between macroscopic stress relaxation and molecular-level chain exchange in triblock copolymer micelles has been explored using rheology and time-resolved small-angle neutron scattering (TR-SANS), marking the first measurements of chain exchange in concentrated triblock networks. It has long been assumed in models of transient or thermoreversible networks that the time scales for these two processes are equal. Experimentally, we find that stress relaxation occurs many orders-of-magnitude faster than chain exchange. This difference is quantitatively explained by modest dispersity in the core block that results in a slight asymmetry within any given nominally symmetric triblock. For stress relaxation to occur, only the shorter chain must pull out, while chain exchange is slowed due to the requirement of the eventual pullout of the longer block. The pullout time is extremely sensitive to the length of the core block. This mechanism is supported by measurements with an intentionally asymmetric triblock copolymer, which displays an even larger difference between the stress relaxation and chain exchange rates. These results establish a quantitative molecular-level picture of the chain dynamics associated with stress relaxation in triblock copolymer networks.

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Research Organization:: University of Minnesota, Twin Cities, MN (United States)

Sponsoring Organization:: NNCI; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704; SC0017809

OSTI ID:: 2520571

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Journal Issue: 3 Vol. 11; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: How Does the Rate of Chain Exchange Relate to Stress Relaxation in Triblock Copolymer Networks?

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