In Situ Hydrolysis of Block Copolymers at the Water‐Oil Interface

In situ manipulation of the chemical composition of block copolymers at the fluid interfaces affords a route by which the interfacial tension, the packing of the copolymers, and the penetration of the blocks into the two liquids can be controlled. Here, a series of linear block copolymers of poly(so...

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Bibliographic Details
Published in:Angewandte Chemie 2022-06, Vol.134 (25), p.n/a
Main Authors: Chen, Zhan, Hu, Mingqiu, Li, Xindi, Smith, Darren M., Seong, Hong‐Gyu, Emrick, Todd, Rzayev, Javid, Russell, Thomas P.
Format: Article
Language:English
Subjects:
Block Copolymers
Chemical composition
Chemistry
Copolymers
Fluorescence
Fluorescence recovery after photobleaching
Glycerol
Hydrolysis
Hydrophobicity
In Situ Hydrolysis
Interface reactions
Interfaces
Molecular weight
Photobleaching
Polymers
Polystyrene resins
Reconfiguration
Self-Assembly
Styrene
Surface tension
Tension
Time dependence
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Summary:In situ manipulation of the chemical composition of block copolymers at the fluid interfaces affords a route by which the interfacial tension, the packing of the copolymers, and the penetration of the blocks into the two liquids can be controlled. Here, a series of linear block copolymers of poly(solketal methacrylate‐b‐styrene) (PSM‐b‐PS) are used, converting hydrophobic PSM block into a hydrophilic glycerol monomethacrylate (GM) block, that results in a marked decrease in the liquid‐liquid interfacial tension. The kinetics of the first‐order hydrolysis reaction was analyzed by monitoring the time‐dependent interfacial tension as a function of pH, polymer concentration, molecular weight, and composition. Fluorescence recovery after photobleaching (FRAP) was used to measure the in‐plane dynamics of the copolymers before and after hydrolysis. This work provides insights into a quantitative pathway by which in situ interfacial reactions may be performed and monitored in real time, completely changing the interfacial activity of the molecule. Real‐time pendant drop tensiometry of a toluene solution of poly(solketal methacrylate‐b‐styrene) (PSM‐b‐PS) in water was measured to monitor the conversion of PSM blocks into glycerol monomethacrylate (GM) blocks upon the addition of acid to the aqueous phase. This work provides opportunities to quantitatively monitor responsive block copolymers for structuring liquids.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202201392