Influence of conformational asymmetry on polymer-polymer interactions: An entropic or enthalpic effect?
Abstract
The order-to-disorder transition (ODT) of 21 compositionally symmetric diblock copolymers consisting of various combinations of poly(ethylene) (PE), poly(ethyl ethylene) (PEE), poly(ethylene−propylene) (PEP), poly(ethylene oxide) (PEO), and poly(dimethylsiloxane) (PDMS) was used as a measure of the strength of the interaction between the polymers. Conformational asymmetry makes a contribution to polymer−polymer thermodynamics that is not explainable within existing simple theories. For a series of PDMS−hydrocarbon diblock copolymers the observed phase behavior can be rationalized through a self-consistent set of solubility parameters. However, this model as well as other models breaks down when the phase behavior of a series of PEO−hydrocarbon block copolymers is included. We suggest that conformational asymmetry leads to an enthalpic contribution to the Flory−Huggins parameter χ through an effective coordination number which is maximized when both of the blocks have large conformational symmetry parameters, β 2 .
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PS-b-PDMS, PS-b-P2VP, and PS-b-PLA are capable of self-assembling into sub-10 nm domain sizes.
“Some other BCPs that are capable of self-assembling into sub-10 nm domain sizes include PS-b-PDMS [125], PS-b-P2VP [126], and PS-b-PLA [118].”
From Block Copolymers: Synthesis, Self-Assembly, and Applications (2017) · cites this paper as [125]
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- Authors
- Almdal, K., Hillmyer, M. A., & Bates, F. S.
- Affiliations
- The Danish Polymer Centre, Risø National Laboratory, P.O. Box 49, DK-4000 Roskilde, Denmark
- University of Minnesota (US)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-08-17
- Volume
- 35
- Issue
- 20
- Pages
- 7685-7691
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2074004582
- Cited by
- 62
- References
- 23
- Citations by year
- 2026: 2 · 2025: 2 · 2024: 3 · 2023: 2 · 2022: 1 · 2021: 5 · 2020: 2 · 2019: 3 · 2018: 1 · 2017: 5 · 2016: 2 · 2015: 2 · 2014: 3 · 2013: 5 · 2012: 4
- FWCI
- 2.80
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Technical University of Denmark, DTU Orbit (Technical University of Denmark, DTU) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- conformational asymmetry, polymer-polymer interactions, order-disorder transition, diblock copolymers, Flory-Huggins interaction parameter, enthalpy contribution, solubility parameter, poly(ethylene oxide), polydimethylsiloxane, polyethylene, block copolymer phase behavior, coordination number
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