Rationalizing the phase behavior of triblock-copolymers through experiments and molecular simulations

German Perez-Sanchez, Filipa A. Vicente, Nicolas Schaeffer, Inês S. Cardoso, Sonia P.M. Ventura, Miguel Jorge, Joao A.P. Coutinho

Research output: Contribution to journalArticle

Abstract

In this paper, we develop a new coarse-grained model, under the MARTINI framework, for Pluronic block copolymers that is able to describe the self-assembly mechanism and reproduce experimental micelle sizes and shapes. Previous MARTINI-type Pluronic models were unable to produce realistic micelles in aqueous solution, and thus our model represents a marked improvement over existing approaches. We then applied this model to understand the effects of polymer structure on the cloud point temperature measured experimentally for a series of Pluronics, including both normal and reverse copolymers. It was observed that high polyoxypropylene glycol content leads to dominant hydrophobic interactions and a lower cloud point temperature, while high hydrophilic polyoxyethylene glycol content shields the micelles against aggregation and hence leads to a higher cloud point temperature. As the concentration increases, the effect of polymer architecture (normal versus reverse) starts to dominate, with reverse Pluronics showing a lower cloud point temperature. This was shown to be due to the increased formation of cross-links between neighboring micelles in these systems, which promote micelle aggregation. Our results shed new light on these fascinating systems and open the door to increased control of their thermal responsive behavior.

Original languageEnglish
Pages (from-to)21224-21236
Number of pages13
JournalJournal of Physical Chemistry C
Volume123
Issue number34
Early online date5 Aug 2019
DOIs
Publication statusPublished - 29 Aug 2019

Fingerprint

Micelles
Phase behavior
Poloxamer
Block copolymers
micelles
copolymers
Glycols
simulation
Experiments
glycols
Polymers
Agglomeration
Temperature
polymers
block copolymers
Self assembly
Polyethylene glycols
temperature
self assembly
Copolymers

Keywords

  • copolymers
  • self-assembly mechanism
  • MARTINI framework
  • polymer structure

Cite this

Perez-Sanchez, G., Vicente, F. A., Schaeffer, N., Cardoso, I. S., Ventura, S. P. M., Jorge, M., & Coutinho, J. A. P. (2019). Rationalizing the phase behavior of triblock-copolymers through experiments and molecular simulations. Journal of Physical Chemistry C, 123(34), 21224-21236. https://doi.org/10.1021/acs.jpcc.9b04099
Perez-Sanchez, German ; Vicente, Filipa A. ; Schaeffer, Nicolas ; Cardoso, Inês S. ; Ventura, Sonia P.M. ; Jorge, Miguel ; Coutinho, Joao A.P. / Rationalizing the phase behavior of triblock-copolymers through experiments and molecular simulations. In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 34. pp. 21224-21236.
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Perez-Sanchez, G, Vicente, FA, Schaeffer, N, Cardoso, IS, Ventura, SPM, Jorge, M & Coutinho, JAP 2019, 'Rationalizing the phase behavior of triblock-copolymers through experiments and molecular simulations', Journal of Physical Chemistry C, vol. 123, no. 34, pp. 21224-21236. https://doi.org/10.1021/acs.jpcc.9b04099

Rationalizing the phase behavior of triblock-copolymers through experiments and molecular simulations. / Perez-Sanchez, German; Vicente, Filipa A.; Schaeffer, Nicolas; Cardoso, Inês S.; Ventura, Sonia P.M.; Jorge, Miguel; Coutinho, Joao A.P.

In: Journal of Physical Chemistry C, Vol. 123, No. 34, 29.08.2019, p. 21224-21236.

Research output: Contribution to journalArticle

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T1 - Rationalizing the phase behavior of triblock-copolymers through experiments and molecular simulations

AU - Perez-Sanchez, German

AU - Vicente, Filipa A.

AU - Schaeffer, Nicolas

AU - Cardoso, Inês S.

AU - Ventura, Sonia P.M.

AU - Jorge, Miguel

AU - Coutinho, Joao A.P.

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